RU2790065C1 - Production of silicon dioxides with large pores and their use in chrome catalysts for olefin polymerization - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chrome catalysts on a carrier (options) and methods for polymerization of olefins in the presence of the specified catalysts (options). The catalyst contains composite based on silicon dioxide and from 0.1 to 15% by wt. of chrome. The specified catalyst is characterized by: volume density from 0.08 to 0.4 g/ml; total pore volume from 0.4 to 2.5 ml/g; specific surface area according to BET method from 175 to 375 m²/g, and maximum pore diameter from 10 to 80 nm, where the maximum pore diameter relates to a location, according to a pore diameter scale, of the highest point on a pore size distribution curve; and (1) where from 0.5 to 40% of the total pore volume of the catalyst is for pores with diameters ranging from 30 to 100 nm, or (2) from 40 to 85% of the total pore volume of the catalyst is fore pores with diameters ranging from 10 to 50 nm, or (3) from 1 to 25% of the total pore volume of the catalyst is for pores with diameters less than or equal to 5 nm; and less than or 4% of the total pore volume of the catalyst is for pores with diameters less than or equal to 3 nm.

EFFECT: invention allows for modification of some physical parameters of a catalyst and substrate, such as a surface area and a pore volume, for regulation or control of important parameters of the molecular weight and branching of polymer, while maintaining high catalytic activity.

34 cl, 11 dwg, 11 tbl, 3 ex

Description

FIELD OF TECHNOLOGY

The present invention generally relates to supported chromium catalysts and titanated chromium catalysts, methods for producing supported catalysts, methods for using said catalysts for the polymerization of olefins, polymer resins made using such catalysts, and articles made using said polymer resins. More specifically, the present invention relates to methods for producing a silica-based composite containing a significant number of large pores (for example, a diameter of more than 10 nm or 30 nm), and the subsequent use of a large-pore silica-based composite for the preparation of supported chromium catalysts. and titanated chromium catalysts.

BACKGROUND OF THE INVENTION

Chromium/silica catalysts and chromium/silica-titanium dioxide catalysts can be used to produce ethylene-based polymers such as HDPE (high density polyethylene). However, the ability to control or control the molecular weight, molecular weight distribution, and degree of long chain branching of such polymers based solely on the physical structure of the catalyst and the silica support has not yet been fully explored. It would be useful to modify certain catalyst and support physical parameters, such as surface area and pore volume, to adjust or control important polymer molecular weight and branching parameters while maintaining high catalytic activity. Accordingly, the present invention as a whole is directed to these purposes.

SUMMARY OF THE INVENTION

This brief description of the present invention is provided to introduce a selection of concepts in a simplified form, which are further presented below in the detailed description. It is implied that this summary is not intended to identify the required or key features of the claimed subject matter. It is also understood that this brief description does not limit the scope of the claimed subject matter.

According to one aspect of the present invention, a method for producing a composite based on silicon dioxide is provided, while according to such an aspect, this method may include (1) combining component I of silicon dioxide and component II of silicon dioxide in a diluent containing at least about 70% of the mass. water to form a mixture; and (2) forming a silica-based composite in said mixture. The silica component I may comprise irregular and non-spherical silica particles typically having an average size ratio of at least about 2:1 and a BET specific surface area ranging from about 150 to about 1000 m ² /g, with the dioxide component II silicon may include colloidal silicon dioxide.

According to another aspect of the present invention, a process is provided for preparing a silica-based composite, wherein according to such an aspect, said method may comprise (1) combining a silica component I and a silica component II in a solvent to form a mixture, and (2) forming a composite in said mixture based on silicon dioxide. The silica component I may comprise irregular and non-spherical silica particles typically having an average size ratio of at least about 2:1 and a BET specific surface area ranging from about 150 to about 1000 m ² /g, with the dioxide component II silicon may include a silicon compound.

According to another aspect of the present invention, a method is provided for preparing a supported chromium catalyst, wherein in such an aspect, said method may include combining (before or during calcination) a chromium-containing compound and an optional titanium-containing compound with a silica-based composite to form a supported chromium catalyst.

According to another aspect of the present invention, there is provided a process for preparing a supported chromium catalyst, wherein in such an aspect, said process may comprise (1) combining a chromium-containing compound and an optional titanium-containing compound with any of the silica component I and silica component II described herein, in a diluent or solvent to obtain a mixture, and (2) obtaining in said mixture a chromium compound on a substrate.

According to another aspect of the present invention, silica-based composites and supported chromium catalysts are also provided, wherein any silica-based composite and supported chromium catalyst described herein can be characterized by a bulk density ranging from about 0.08 to about 0.4 g/ml, total pore volume from about 0.4 to about 2.5 ml/g, BET surface area from about 175 to about 375 m ² /g, and maximum pore diameter from about 10 to about 80 nm. Typically, the maximum pore diameter of the supported silica-chromium catalyst composite may be from about 15 nm to about 60 nm, from about 15 nm to about 50 nm, or from about 17 nm to about 40 nm. In addition, the total pore volume of the supported silica-chromium catalyst composite in pore diameters less than or equal to 5 nm may be less than or about 25%, or less than or about 20%, for example, from about 2 to about 15 %, and/or the total pore volume of the supported silica-chromium catalyst composite in pores with diameters less than or equal to 3 nm may be less than or about 8%, less than or about 6% or less or about 4%. Additionally or alternatively, the total pore volume of the supported silica-chromium catalyst composite in pore diameters ranging from 30 to 100 nm can be from about 0.5 to about 40%, for example, from about 1 to about 35%, or from about 2 to about 35%.

The present invention also contemplates and includes processes for the polymerization of olefins. Such methods may include contacting a supported (activated) chromium catalyst and an optional co-catalyst with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

In both the above summary and the following detailed description, examples are given, the descriptions themselves being illustrative only. Accordingly, the foregoing summary and the following detailed description should not be construed as limiting. In addition, features or variations in addition to those set forth herein may be provided. For example, some aspects may relate to various combinations and subcombinations of the features discussed in the detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

In FIG. 1-7 are plots of pore volume distribution versus pore diameter (nm) for fumed silica, fumed silica, and silica-based composites made from fumed silica and fumed silica according to Example 1.

In FIG. 8-11 are plots of pore volume distribution versus pore diameter (nm) for silicate oligomer, fumed silica, and silica composites prepared from silicate oligomer and fumed silica according to Example 2.

DEFINITIONS

For a clearer understanding of the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present description. If any term is used in the description which is not specifically defined herein, the definition given in the IUPAC Compendium of Chemical Terminology, ^2nd Ed (1997) may be used, provided that such definition does not conflict with any other description or definition. used herein, or does not render undefined or invalidate any claim to which this definition refers. In the event that any definition or use given in any document incorporated herein by reference conflicts with the definition or use given herein, the definition or use given herein shall take precedence.

In this document, the features of the subject matter are described in such a way that, within specific aspects, a combination of various features can be envisaged. For each and every aspect and each and every feature described herein, all combinations that do not adversely affect the compounds, compositions, processes or methods described herein are discussed with or without detailed description of the specific combination. In addition, unless expressly stated otherwise, any aspect or feature described herein can be combined to describe compounds, compositions, processes or methods according to the present invention that do not contradict the present invention.

In general, groups of elements are indicated using the numbering scheme given in the version of the Periodic Table of the Elements published in Chemical and Engineering News , 63(5), 27, 1985. In some cases, a group of elements may be indicated using the common name adopted for a given groups; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.

The term "hydrocarbon" as used in the present specification and claims refers to a compound containing only carbon and hydrogen, whether the compound is saturated or unsaturated. Other identifiers can be used to indicate the presence of specific groups in a hydrocarbon (eg, halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). In this document, the term "hydrocarbyl group" is used as defined by IUPAC: a monovalent group formed by removing a hydrogen atom from a hydrocarbon (ie, a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include, among other groups, alkyl, alkenyl, aryl, and aralkyl groups.

For any particular compound or group described herein, any given name or structure (general or specific) is intended to include all conformational isomers, regioisomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents, unless otherwise noted. . The name or structure (general or specific) also includes all enantiomers, diastereomers and other optical isomers (if any), whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as will be understood by the skilled artisan, unless otherwise indicated. For example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a t-butyl group.

Unless otherwise indicated, the term "substituted" when used to describe a group, for example when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces hydrogen in that group and is intended to be non-limiting. In addition, unless otherwise indicated, a group or groups may also be referred to herein as "unsubstituted" or using equivalent terms such as "unsubstituted", which term refers to the parent group in which a non-hydrogen moiety does not replace an atom hydrogen within such a group. In addition, unless otherwise indicated, the term "substituted" is meant to be non-limiting and includes inorganic substituents or organic substituents, as understood by a person skilled in the art.

As used herein, the terms “contacting” and “combining” are used to describe compositions, processes, and methods in which materials or components are brought into contact or combined with each other in any order, in any manner, and for any period of time, unless otherwise indicated. For example, the materials or components may be mixed, agitated, suspended, dissolved, brought into contact, processed, companded, or otherwise brought into contact or combined in any other way or using any suitable method or technology.

Although compositions (e.g., composites), processes, and methods are described herein in terms of "comprising" various components or steps, said compositions (e.g., composites), processes, and methods may also "consist essentially of" or " consist of" various components or steps unless otherwise noted.

Singular terms are meant to include plural alternatives, such as at least one. For example, the description of "colloidal silicon dioxide", "chromium-containing compound", etc. is meant to be includes one colloidal silicon dioxide, one chromium-containing compound, or mixtures or combinations of more than one colloidal silicon dioxide, chromium-containing compound, etc., unless otherwise indicated.

The term "polymer" is used herein in a general sense and includes olefin homopolymers, copolymers, terpolymers, and the like, as well as their alloys and mixtures. The term "polymer" also includes impact copolymers, block copolymers, graft, random and alternating copolymers. The copolymer can be made from an olefin monomer and one olefin comonomer, while the terpolymer can be made from an olefin monomer and two olefin comonomers. Accordingly, "polymer" includes copolymers and terpolymers. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Therefore, an ethylene polymer will include ethylene homopolymers, ethylene copolymers (eg, ethylene/α-olefin copolymers), ethylene terpolymers, and the like, as well as combinations or mixtures thereof. Thus, ethylene polymer includes polymers often referred to in the art as LLDPE (Linear Low Density Polyethylene) and HDPE (High Density Polyethylene). For example, an ethylene copolymer can be made from ethylene and a comonomer such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene/1-hexene copolymer. The term "polymer" also includes all possible geometric configurations, if present and unless otherwise indicated, such configurations may include isotactic, syndiotactic and random symmetries. In addition, the term "polymer" is intended to include polymers of any molecular weight, and also includes lower molecular weight polymers or oligomers.

The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. do not depend on the actual product or composition resulting from the contact or interaction of the initial components of the proposed or claimed catalyst composition/mixture/system, the nature of the active catalytic site, or the fate of the co-catalyst or catalyst on the support after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. includes the original starting components of the composition, as well as any product(s) that may be formed as a result of bringing into contact of these initial starting components, and this includes both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. may be used interchangeably herein.

"Water-soluble" substance means that the specified substance is soluble in water at standard temperature (25 ^about C) and pressure (1 atm (about 101 kPa)); in this case, no precipitation of the substance in water is visually observed. Similarly, "solution" means no visible precipitate at standard temperature and pressure.

Various ranges of numerical values are given in this document. When a range of any type is given or claimed, the intent is to describe or claim individually every possible number that can reasonably be included in such a range, including the endpoints of the range, and any subranges and combinations of subranges included therein. , unless otherwise specified. As a typical example, it is reported herein that the total pore volume of a silica composite (or supported catalyst) according to aspects of the present invention may be from about 0.5 to about 3.5 ml/g. In stating that the total pore volume may be from about 0.5 to about 3.5 ml/g, the intent is to indicate that the pore volume may be any pore volume within the range given and, for example, may be equal to about 0.5, about 1, about 1.5, about 2, about 2.5, about 3, or about 3.5 ml/g. In addition, the total pore volume can be in any range from about 0.5 to about 3.5 ml/g (for example, from about 0.7 to about 2.5 ml/g), this range also includes any combination ranges from about 0.5 to about 3.5 ml/g (for example, the pore volume may be from about 0.5 to about 1 ml/g, or from about 2 to about 3 ml/g). In addition, in all cases where "about" a specific value is indicated, such value is described in itself. Thus, the statement that the total pore volume can be from about 0.5 to about 3.5 ml/g also indicates a total pore volume from 0.5 to 3.5 ml/g (for example, from 0.7 to about 3.5 ml/g). 2.5 ml/g), while the specified range also includes any combination of ranges from 0.5 to 3.5 ml/g (for example, the pore volume can be from 0.5 to 1 ml/g or from 2 to 3 ml /G). Likewise, all other ranges described herein should be interpreted in the same way as the example provided.

The term "about" means that quantities, sizes, compositions, parameters and other quantitative indicators and characteristics are not and should not be exact, but may have an approximate value, including more or less, if necessary, reflecting tolerances, conversion factors , rounding off, measurement errors, and the like, as well as other factors known to those skilled in the art. In general, an amount, size, composition, parameter, or other quantity or characteristic is "exemplary" or "approximate" whether or not it is explicitly stated. The term "about" also includes amounts that differ due to different equilibrium conditions for the composition obtained from a particular initial mixture. Whether such meaning is modified by the term "about" or not, the claims include equivalents to such quantities. The term "about" may mean within 5% of the numerical value given.

While any methods, devices, and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, exemplary methods, devices, and materials are described herein.

All publications and patents referenced herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the concepts and methodologies described in the publications that can be used in conjunction with the invention described herein.

DETAILED DESCRIPTION OF THE INVENTION

This document describes methods for preparing composites based on silica and chromium catalysts on a substrate. In such methods, "skeleton" silica or "skeleton" silica, typically characterized by irregular and non-spherical silica particles (e.g., fumed silica), is combined with "glue" silica (e.g., colloidal silica) to form composite (or aggregate) structure of silicon dioxide, having a large surface area and containing pores with a large diameter. Surprisingly, in general, the individual silica components are by themselves not suitable for use in supported polymerization catalysts, however, by combining the components described herein, excellent supported catalysts are obtained despite relatively low overall pore volumes and areas. surfaces. In addition, silica-based composites and supported chromium catalysts can be synthesized in water-based systems, thereby reducing VOCs and emissions.

Catalysts with large pore diameters can advantageously improve potential melt flow index, which allows polymers with higher melt flow index, as well as increased catalytic activity and reduced levels of long chain branching in the polymer.

METHODS FOR OBTAINING COMPOSITES BASED ON SILICON DIOXIDE

Aspects of the present invention relate to methods for preparing a silica composite (or silica composition). The first method may include (or consist essentially of, or consist of) (1) combining component I of silicon dioxide and component II of silicon dioxide in a diluent containing at least about 70% of the mass. water to form a mixture; and (2) forming in said mixture a (co-thickened) silica composite. In the first method, the silica component I may comprise irregular and non-spherical silica particles typically having an average size ratio of at least about 2:1 and a BET specific surface area ranging from about 150 to about 1000 m ² /g, wherein the silica component II may include colloidal silica. The second process may include (or consist essentially of, or consist of) (1) combining the silica component I and the silica component II in a solvent to form a mixture, and (2) forming in said mixture a (co-thickened) silica-based composite silicon. In the second method, the silica component I may comprise irregular and non-spherical silica particles typically having an average size ratio of at least about 2:1 and a BET specific surface area ranging from about 150 to about 1000 m ² /g, wherein the silica component II may include a silicon compound (or a silicon-containing compound). In the first and second methods, the resulting silica composite can generally be characterized by a bulk density in the range of about 0.08 to about 0.4 g/ml, a total pore volume of from about 0.4 to about 2.5 ml/g , a BET specific surface from about 175 to about 375 m ² /g, and a maximum pore diameter from about 10 to about 80 nm, among other properties described herein.

In general, the features of the first method and the second method are independently described herein (e.g., but not limited to, the properties and characteristics of the silica component I, the properties and characteristics of the silica component II, the conditions under which the silica composite is prepared, and properties and characteristics of the silica composite), and such features can be combined in any combination to further describe the proposed methods for obtaining a composite based on silicon dioxide. Moreover, additional processing steps can be performed before, during and/or after any of the steps in any of the methods described herein, and used without limitation and in any combination to further describe the proposed methods, unless otherwise indicated. In addition, any silica-based composites obtained in accordance with the claimed methods are within the scope of the present invention and included in it. Moreover, silica components (or compositions) having a bulk density ranging from about 0.08 to about 0.4 g/mL, a total pore volume of from about 0.4 to about 2.5 mL/g, a specific surface area of BET method from about 175 to about 375 m ² /g and a maximum pore diameter from about 10 to about 80 nm, are included in this document regardless of the method of their preparation.

Turning now to the first method of obtaining a composite based on silicon dioxide, this method may include (1) the combination of component I of silicon dioxide and component II of silicon dioxide in a diluent containing at least about 70% of the mass. water to form a mixture; and (2) forming in said mixture a (co-thickened) silica composite. The silica component I may comprise irregular and non-spherical silica particles having an average size ratio of at least about 2:1 and a BET specific surface in the range of from about 150 to about 1000 m ² /g, with the silica component II may include colloidal silicon dioxide. In contrast to typical spherical silica particles, silica component I typically contains irregular and non-spherical silica particles. Such particles can be described as irregular, lamellar or non-spherical, as well as having other shapes/morphologies. Typical silica-based materials that can be used as the silica component I may include highly dispersed silicas (pyrogenic silicas), diatomite materials, silica-rich clays (e.g., montmorillonite), and the like, as well as combinations thereof. . According to some aspects of the present invention, the silica component I may be non-porous.

The BET specific surface area of the silica component I is not particularly limited and is typically about 150 to about 1000 m ² /g. For example, the BET specific surface area may be from about 150 to about 600 m ² /g, or alternatively from about 200 to about 500 m ² /g. Likewise, the average aspect ratio of silica component I is not particularly limited, but is generally at least about 2:1. Most often, the average aspect ratio of silica component I is at least about 3:1, at least about 5:1, or at least about 10:1. Average size ratio ranges for silica component I include ranges from about 2:1 to about 50:1, from about 3:1 to about 50:1, and from about 5:1 to about 50:1. As used herein, size ratio refers to the longest (measurable) particle size divided by the shortest size. Optionally, silica component I can be further characterized by an average particle size d50 of about 5 to about 500 nm, or about 10 to about 300 nm.

According to specific aspects of the present invention, the silica component I may include fumed silica, with suitable grades being commercially available under the designations Cab-o- ^sil® fumed silica, Aerosil ^® fumed silica, and etc. As silica component I, combinations of more than one highly dispersed silica can be used, regardless of the supplier.

In the first method, the silica component II may comprise fumed silica, with suitable grades being commercially available under the terms ^Ludox® fumed silica, Nyacol ^® fumed silica, Levisil fumed silica, and the like. Combinations of more than one colloidal silica can be used as the silica component II, regardless of the supplier. Colloidal silicas are usually supplied as solids in liquids. Any suitable % solids may be used.

As a rule, colloidal silicon dioxide has an essentially spherical shape, in contrast to component I of silicon dioxide. Average size ratios for colloidal silica are typically less than 1.8:1, less than 1.5:1, or less than 1.25:1, but are not limited to them. The average particle sizes (d50) of colloidal silica are relatively small and typically range from about 3 to about 25 nm, from about 3 to about 18 nm, or from about 4 to about 15 nm. Illustrative and non-limiting ranges of BET specific surface area of colloidal silica may include ranges from about 200 to about 1000 m ² /g, from about 225 to about 500 m ² /g, and from about 250 to about 450 m ² /g.

The relative amounts of the silica component I and the silica component II in the first method are not particularly limited as long as the amount of the silica component II (adhesive component) is sufficient to obtain a suitable silica composite. Thus, silica component II is generally used in smaller amounts compared to silica component I. The amount of silica component II, based on the total amount of silica component I and silica component II, can be from about 1 to about 35% by weight; alternatively from about 2 to about 25% of the mass.; alternatively from about 5 to about 30% of the mass.; or alternatively from about 3 to about 20% of the mass. In the case of colloidal silicon dioxide, the amount of water is excluded from this calculation.

At stage (1) of the first method component I of silicon dioxide and component II of silicon dioxide can be brought into contact or combined in a diluent containing at least 70% of the mass. water to form a mixture. It may be useful to use a diluent that essentially consists entirely of water or contains at least about 80 wt. -%, at least about 90 wt. -%, at least about 95 wt. water. The silica component I, the silica component II and the diluent may be brought into contact or combined in any order or sequence.

Turning now to step (2), in which a silica-based composite is produced in said mixture or a co-thickened silica-based composite is obtained in said mixture. The formation or co-gelling of the silica composite can be accomplished using a variety of methods such as adjusting the pH of the mixture (e.g., adding an acid or base), removing water from the mixture and/or heating the mixture, adding a metal ion (e.g., Al, Fe, Cr), adding an organic solvent (eg, alcohol) to the mixture, storing the mixture for a suitable period of time, etc., or using any combination of these methods. For example, combining the silica components in step (1) to form a mixture may spontaneously lead to the formation of a silica composite, and thus step (1) and step (2) can occur substantially simultaneously. As another example, adding alcohol to the resulting mixture (or adding the resulting mixture to alcohol) can result in the formation of a silica-based composite. As another example, changing the pH of a mixture by adding an acid (or base) can result in the formation of a silica composite. Other suitable methods for forming or co-gelling silica-based materials are known in the art and are also included herein.

Turning now to a second method for preparing a silica composite, said method may include (1) combining the silica component I and the silica component II in a solvent to form a mixture, and (2) forming in said mixture a (co-thickened) silica composite silicon. In the second method, the silica component I may comprise the irregular and non-spherical silica particles described herein, and thus the silica component I may include any suitable fumed silica, such as Cab-o-sil® fumed silica ^. (Cab-o-force), highly dispersed silicon dioxide Aerosil ^® (Aerosil), and the like, as well as combinations thereof. In the second method, the silica component II may include a silicon compound (or a silicon-containing compound).

The specific silicon compound used as the silicon component II is not particularly limited. Representative and non-limiting examples of suitable silicon compounds may include silicon alkoxide (eg, tetraethyl orthosilicate), silicon halide, silicon hydride, silane, hydrocarbylsilane, siloxane, and the like, and combinations thereof. According to one aspect, for example, the silicon compound may include sodium silicate, ethyl silicate, silicate oligomer (eg, ethyl silicate oligomer), and any combination thereof, while in another aspect, the silicon compound may include Silbond ^® silicate (Silbond).

Similarly, any suitable solvent can be used in the second method, but often such a solvent is miscible with both oil and water. Representative and non-limiting examples of suitable solvents may include a ketone (e.g. acetone), alcohol (e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, etc.), glycol, ester, ether, acetonitrile, etc. .P. In addition, combinations of two or more solvents may be used. The solvent may also additionally contain water, so that the solvent used may, for example, be a mixture of alcohol and water.

The relative amounts of the silica component I and the silica component II in the second method are not particularly limited as long as the amount of the silica component II (adhesive component) is sufficient to form a suitable silica composite. The amount of silica component II, based on the total amount of silica component I and silica component II, can be from about 10 to about 90% by weight; alternatively from about 15 to about 60% of the mass.; alternatively from about 20 to about 80% of the mass.; or alternatively from about 20 to about 50% of the mass.

Referring now to step (2), in which a silica composite is produced in said mixture or a co-thickened silica composite is obtained in said mixture. The formation or co-gelling of the silica composite can be accomplished using various techniques described herein for the first method, any of the techniques listed being equally applicable to the second method.

Steps (1) and (2) of the first and second methods can be carried out at any suitable temperature and for any suitable period of time. Typical and non-limiting temperature ranges may include from about 5°C to about 80°C, from about 15°C to about 60°C, from about 10°C to about 40°C, or from about 20°C to about 50°C. . Such temperature ranges are also intended to include cases in which the respective step is carried out at a series of different temperatures rather than at one fixed temperature lying within the respective temperature ranges.

Likewise, the time period for the respective step is not particularly limited, and said step can be carried out for any suitable time period. In some aspects, such time period may be at least about 1 minute, at least about 5 minutes, at least about 10 minutes, at least about 15 minutes, or at least about 30 minutes. In other aspects, such time period may be from about 30 seconds to about 48 hours, from about 1 minute to about 24 hours, from about 5 minutes to about 8 hours, from about 15 minutes to about 8 hours, or from about 5 minutes to about 2 hours.

The first method and the second method may include the step of drying the silica composite; alternatively, the step of calcining the silica composite; or alternatively a step of drying the silica composite and a step of calcining the silica composite. Any drying method or technique may be used, such as drying at elevated temperature and subatmospheric pressure, spray drying, and the like. Typical maximum calcination temperatures are often from about 200°C to about 800°C, such as from about 250°C to about 600°C, from about 300°C to about 600°C, or from about 300°C to about 500°C. C. According to these and other aspects, such temperature ranges are also intended to include cases in which the calcination step is conducted at a series of different temperatures (e.g. initial calcination temperature, maximum calcination temperature) rather than at one fixed temperature within the respective ranges.

The duration of the calcination step is not limited to any particular time period. Therefore, the calcination step can be carried out, for example, for a period of time ranging from 30-45 minutes to 36-48 hours or more. A suitable calcination time may depend on, for example, the initial/maximum calcination temperature, among other variables. However, in general, the calcination step can be carried out over a period of time that can be from about 30 minutes to about 48 hours, for example, from about 1 hour to about 24 hours, from about 1 hour to about 12 hours, from about 2 hours up to about 12 hours, or from about 2 hours to about 8 hours.

The calcination step can be carried out in a calcination gas stream containing (or consisting essentially of, or consisting of) an inert gas (eg, nitrogen), oxygen, air, or any mixture or combination thereof. In some aspects, the calcination gas stream may contain air, while in other aspects, the calcination gas stream may contain a mixture of air and nitrogen. However, in some aspects, the calcining gas stream may be an inert gas such as nitrogen and/or argon.

The calcination step can be carried out using any suitable method and equipment, either batchwise or continuously. For example, the calcination step can be carried out in a belt kiln or alternatively in a rotary kiln. In some aspects, the calcination step may be carried out in a batch or continuous calcination vessel containing a fluidized bed. As will be appreciated by those skilled in the art, other suitable methods and equipment may be used for the calcination step, and such methods and equipment are included herein.

Optionally, the titanium-containing compound may be contacted or combined, in any order, with the silica component I and the silica component II in a diluent or solvent in step (1) of the first method and the second method, for example, to form a silica composite ( e.g. "titanized" silica composite). The specific titanium-containing compound used is not particularly limited. In accordance with some aspects of the present invention, the titanium compound may be a Ti(III) compound and/or a Ti(IV) compound. Representative and non-limiting examples of suitable titanium-containing compounds may include titanium alkoxide (e.g., titanium isopropoxide, titanium n-propoxide), titanium halide, titanium halide or oxohalide, titanium acetylacetonate complex, titanium triethanolamine complex, titanium carboxylate (e.g., oxalate, citrate, lactate, and etc.), etc., as well as their chelated or modified variants to provide better applicability in water-based systems. Combinations of more than one titanium-containing compound can be used in the first method and the second method.

METHODS FOR PRODUCING CHROMIUM CATALYSTS ON A SUBSTRATE

Aspects of the present invention also relate to processes for the preparation of supported chromium catalysts. In the processes for preparing the silica composite described above, the addition of chromium may be included in the respective processes. In one aspect, for example, the third method of the present invention may include (1) combining (in any order) a chromium-containing compound and an optional titanium-containing compound with a silica component I and a silica component II in a diluent or solvent to form a mixture, and ( 2) obtaining in the specified mixture of chromium compounds on the substrate. In such a third process, the silica component I, silica component II, diluent, solvent, and any process conditions may be the same as those described above for the first method and the second method. The components in the combining step may be brought into contact or combined by any suitable means such as mixing or suspending the components. Although not required, it may be useful for the chromium compound (and the titanium compound, if used) to be soluble in the diluent or solvent. In the third method, any suitable temperatures and times may be used, such as those described above for the first and second methods. Optionally, the third method may further include the step of drying the chromium catalyst on the support, the step of calcining the chromium catalyst on the support, or both drying and calcining the chromium catalyst on the support.

The fourth method for producing a supported chromium catalyst according to the present invention may include using the above-described silica-based composite, for example, obtained by performing steps (1) and (2) in the first method or the second method, and (3) combining (in any order ) a chromium-containing compound and an optional titanium-containing compound with a silica-based composite to form a supported chromium catalyst. The components in step (3) may be brought into contact or combined by any suitable means such as mixing or suspending the components. Although not required, it may be useful that the chromium compound (and the titanium compound, if used) be soluble in any liquid medium present during step (3). In the fourth method, any suitable temperatures and times may be used, such as those described above for the first and second methods. Optionally, the fourth method may further include the step of drying the chromium catalyst on the support, the step of calcining the chromium catalyst on the support, or both drying and calcining the chromium catalyst on the support.

The fifth method for producing a supported chromium catalyst according to the present invention may include using the above-described silica-based composite, for example, obtained by performing steps (1) and (2) in the first method or the second method, and (3) combining (in any order ) a chromium-containing compound and an optional titanium-containing compound with a silica-based composite upon calcination to form a supported chromium catalyst. In the fifth method, chromium is introduced into the catalyst during the calcination step to form a supported activated chromium catalyst. Typical and non-limiting examples of a chromium-containing compound include chromium (III) acetate, basic chromium (III) acetate, chromium (III) acetylacetonate, Cr ₂ (SO ₄ ) ₃ , Cr(NO ₃ ) ₃ , and CrO ₃ , and combinations thereof.

In the third, fourth, and fifth processes, the supported chromium catalyst obtained can generally be characterized by a bulk density in the range of about 0.08 to about 0.4 g/ml, a total pore volume of about 0.4 to about 2.5 ml/ g, a BET surface area from about 175 to about 375 m ² /g, and a maximum pore diameter from about 10 to about 80 nm, among other properties described herein.

In general, the features of the third, fourth, and fifth methods are independently described herein (e.g., but not limited to, properties and characteristics of silica component I, properties and characteristics of silica component II, conditions under which a supported catalyst, a chromium-containing compound, a titanium-containing connection (when used), as well as the properties and characteristics of the supported chromium catalyst), and such features can be combined in any combination to further describe the proposed methods for obtaining a supported chromium catalyst. Moreover, additional processing steps can be performed before, during and/or after any of the steps in any of the methods described herein, and used without limitation and in any combination to further describe the proposed methods, unless otherwise indicated. In addition, any supported chromium catalysts (eg, chromium/silica or chromium/silica-titanium dioxide, when using titanium) made in accordance with the proposed methods are within the scope of the present invention and are included therein.

Also included in the present invention are supported chromium catalysts (with or without titanium) having a bulk density in the range of about 0.08 to about 0.4 g/ml, a total pore volume of about 0.4 to about 2, 5 ml/g, BET surface area from about 175 to about 375 m ² /g and a maximum pore diameter from about 10 to about 80 nm, and containing a composite based on silicon dioxide and usually from about 0.1 to about 15% mass. chromium, regardless of how they are obtained. Thus, in accordance with aspects of the present invention, the amount of the silica-based composite in the supported catalyst may generally be from about 85 to about 99.9 wt %. alternatively from about 92 to about 99% of the mass.; alternatively from about 93 to about 98% of the mass.; or alternatively from about 94 to about 99% of the mass. The weight percentages given are based on the weight of the silica composite relative to the total weight of the catalyst. The supported chromium catalyst includes catalyst precursors or pre-calcined catalysts (before calcination) as well as activated catalysts or calcined catalysts (after calcination).

Any suitable chromium-containing compound (or chromium precursor) can be used to form a supported chromium catalyst. Illustrative and non-limiting examples of chromium(II) compounds may include chromium(II) acetate, chromium(II) chloride, chromium(II) bromide, chromium(II) iodide, chromium(II) sulfate, and the like, and combinations thereof. . Likewise, illustrative and non-limiting examples of chromium(III) compounds may include chromium(III) carboxylate, chromium(III) naphthenate, chromium(III) halide, chromium(III) sulfate, chromium(III) nitrate, chromium(III) dionate, and etc., as well as their combinations. In some aspects, the chromium-containing compound may include chromium(III) acetate, chromium(III) acetylacetonate, chromium(III) chloride, chromium(III) bromide, chromium(III) sulfate, chromium(III) nitrate, and the like, and their combinations.

When used, any suitable titanium-containing compound can be used, such as titanium alkoxide (e.g. titanium isopropoxide, titanium n-propoxide), titanium halide, titanium halide or oxohalide, titanium acetylacetonate complex, titanium triethanolamine complex, titanium carboxylate (e.g. oxalate, citrate , lactate, etc.), etc., as well as their chelated or modified variants for better applicability in water-based systems. Combinations of more than one titanium-containing compound can be used in the third, fourth and fifth methods. A supported chromium catalyst prepared using a titanium-containing compound may often be referred to as a titanated chromium catalyst (eg, chromium/silica-titanium dioxide).

According to various aspects included in the present invention, a calcination step (often referred to as an activation step) is used. As regards the calcination (or activation) of the supported chromium catalyst, said calcination process can be carried out at various temperatures and times, which are generally chosen to convert all or part of the chromium to hexavalent chromium. Often such a process is carried out in an oxidizing atmosphere, but this is not a requirement. For example, the calcination step may be performed at a maximum temperature in the range of about 400°C to about 1000°C; alternatively from about 500°C to about 900°C; from about 500°C to about 900°C; alternatively from about 600°C to about 871°C; alternatively from about 550°C to about 850°C; alternatively from about 700°C to about 850°C; alternatively from about 725°C to about 900°C; alternatively from about 725°C to about 871°C; alternatively from about 725°C to about 850°C; alternatively from about 750°C to about 871°C; or alternatively from about 750° C. to about 850 ^° C. According to these and other aspects, such temperature ranges are also meant to include instances in which the calcination step is conducted at a series of different temperatures (e.g., start temperature, maximum temperature) rather than at one fixed temperature lying in the appropriate ranges. For example, the calcination step may begin at an initial temperature and then the temperature may be increased to a maximum temperature, such as a maximum temperature in the range of about 550°C to about 850°C, or from about 725°C to about 900°C.

The duration of the calcination step is not limited to any particular time period. Therefore, said calcination step can be carried out, for example, for a period of time ranging from 1 minute to 12-24 hours or more. A suitable calcination time may depend on, among other variables, for example the initial/maximum temperature. However, in general, the calcination step may be carried out over a period of time, which may be from about 1 minute to about 24 hours, for example, from about 30 minutes to about 8 hours, from about 1 hour to about 12 hours, from about 2 hours to about 12 hours, from about 3 hours to about 10 hours, or from about 5 hours to about 10 hours.

In use, the amount of titanium in the supported chromium catalysts (or silica-based composites such as silica-titania) described herein is not particularly limited. However, in general, the amount of titanium in the supported chromium catalyst (or silica composite) can be from about 0.1 to about 20% by weight; alternatively from about 0.5 to about 10% wt.; alternatively from about 1 to about 10% of the mass.; alternatively from about 1 to about 6% of the mass.; or alternatively from about 1.5 to about 5% of the mass. The weight percentages given are based on the amount of titanium relative to the total weight of the catalyst (or silica composite).

Similarly, the amount of chromium in the supported chromium catalysts (pre-calcined or calcined/activated) described herein is not particularly limited. However, in general, the amount of chromium in the supported catalyst may be from about 0.1 to about 20% by weight; alternatively from about 0.1 to about 15% wt.; alternatively from about 0.5 to about 15% wt.; alternatively from about 0.5 to about 5% wt.; alternatively from about 0.5 to about 2.5% wt.; alternatively from about 1 to about 10% of the mass.; or alternatively from about 1 to about 6% of the mass. The weight percentages given are based on the amount of chromium relative to the total weight of the catalyst.

According to one aspect, at least about 75 wt%, at least about 80 wt%, at least about 85 wt%, at least about 90 wt%, at least about 95 wt%. or at least about 99% of the mass. chromium may be present in an oxidation state of three or less. In this aspect, the catalyst is typically pre-calcined, although usually dried. According to another aspect, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least at least about 80% wt., at least about 90% of the mass. or at least about 95% of the mass. chromium may be present as hexavalent chromium. In such an aspect, the catalyst is calcined (or activated).

Turning now to the performance of the supported silica-based and chromium-catalyzed composites described herein, such supported silica-based and chromium-catalyzed composites can be characterized by a bulk density of about 0.08 to about 0.4 g/mL, total volume a pore from about 0.4 to about 2.5 ml/g, a BET specific surface area from about 175 to about 375 m ² /g, and a maximum pore diameter from about 10 to about 80 nm. The illustrative and non-limiting examples of supported silica-chromium catalyst composites of the present invention may also have any of the properties listed below and in any combination unless otherwise indicated.

In one aspect, the bulk density of the silica-chromium catalyst composite on the support may independently be from about 0.08 to about 0.35 g/mL, from about 0.1 to about 0.35 g/mL, from about 0 1 to about 0.32 g/mL, from about 0.12 to about 0.34 g/mL, or from about 0.14 to about 0.37 g/mL. For comparison, a typical bulk density of highly dispersed silicas is in the range of 0.04 to 0.05 g/ml.

The total pore volume and BET specific surface area of suitable supported silica-chromium-catalyzed composites are not particularly limited. The total pore volume may be from about 0.5 to about 3.5 ml/g; alternatively from about 0.4 to about 2.5 ml/g; alternatively from about 0.4 to about 1.5 ml/g; alternatively from about 0.5 to about 2 ml/g; or alternatively from about 0.5 to about 1.3 ml/g. The BET specific surface area can be from about 175 to about 360 m ² /g; alternatively from about 190 to about 375 m ² /g; alternatively from about 200 to about 375 m ² /g; or alternatively from about 200 to about 360 m ² /g.

The silica-based composite and the supported chromium catalyst advantageously contain a significant amount of mesopores (pores greater than or equal to 10 nm in diameter and in particular 30 nm or more). One indicator for quantifying a significant number of large pores is the maximum pore diameter (location, on the pore diameter scale, of the highest point on the pore size distribution curve). The maximum pore diameter of the supported silica-chromium catalyst composite is often independently about 10 to about 80 nm, such as about 10 to about 70 nm, about 10 to about 50 nm, or about 10 to about 40 nm. In some aspects, the maximum pore diameter may be from about 15 to about 60 nm, from about 15 to about 50 nm, from about 17 to about 40 nm, from about 20 to about 80 nm, from about 20 to about 50 nm, or from about 25 nm to about 60 nm.

Another indicator of a significant number of large pores is the average pore diameter (4×PV/SA) (PV - pore volume, SA - surface area). For example, a silica composite with a total pore volume of 1.15 ml/g and a total BET surface area of 359 m ² /g corresponds to an average pore diameter of 12.8 nm. The average pore diameter of the silica-chromium catalyst composite on the support may independently be from about 8 to about 70 nm, from about 9 to about 50 nm, from about 9 to about 30 nm, from about 10 to about 50 nm, or from about 10 to about 30 nm.

Another indicator of a significant number of large pores is the percentage of total pore volume in pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm). Such a percentage of total pore volume in pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm) in a silica composite and supported chromium catalyst can independently be at least about 35%, at least at least about 40%, from about 35% to about 95%, or from about 40% to about 85%.

Another indicator of a significant number of large pores is the percentage of total pore volume in pores with diameters in the range of 30 to 100 nm, ie pore diameters of at least 30 nm and up to 100 nm. Such a percentage of the total pore volume in pores with diameters from 30 to 100 nm in a composite based on silica and a chromium catalyst on a support can independently be from about 0.5 to about 40%, from about 0.5 to about 35%, from about 1 to about 35%, or about 2 to about 35%.

Another indicator of a significant number of large pores is the pore volume value, which characterizes pores with diameters in the range from 10 to 50 nm (or in the range from 10 to 100 nm). The pore volume of pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm) in the silica-based composite and supported chromium catalyst can independently be at least about 0.2 ml/g, at least about 0.3 ml/g, from about 0.2 to about 1.5 ml/g, or from about 0.4 to about 1.3 ml/g.

Another indicator of a significant number of large pores is the percentage of total BET surface area in pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm). Such a percentage of the total surface area in pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm) in a silica-based composite and a supported chromium catalyst can independently be at least about 15%, at least at least about 20%, from about 15% to about 65%, or from about 20% to about 60%.

Another indicator of a significant number of large pores is the BET specific surface area, which characterizes pores with diameters in the range from 10 to 50 nm (or in the range from 10 to 100 nm). The surface area of pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm) in the silica-based composite and supported chromium catalyst can independently be at least about 40 m ² /g, at least about 50 m ² /g, from about 40 to about 200 m ² /g, or from about 60 to about 180 m ² /g.

Given the increased pore volume and surface area in large pores, micropores (less than 10 nm, and in particular less than 5 nm or 3 nm) have a lower pore volume and surface area. In one aspect, for example, the percentage of total pore volume in pores with diameters less than or equal to 10 nm in a silica-based composite and a supported chromium catalyst may independently be less than or about 65%, less than or about 60%, of about 5% to about 65%, or about 15% to about 55%. Additionally or alternatively, the percentage of total pore volume in pores with diameters less than or equal to 5 nm in the silica-based composite and supported chromium catalyst can independently be less than or about 25%, less than or about 20%, from about 1 to about 25% or from about 2 to about 15%. Additionally or alternatively, the percentage of total pore volume in pores with diameters less than or equal to 3 nm in the silica-based composite and supported chromium catalyst can independently be less than or about 8%, less than or about 7%, less than or about 6 % or less, or about 4%.

Similarly, in the case of surface area, the percentage of surface area in pores with diameters less than or equal to 5 nm in a silica-based composite and a supported chromium catalyst can independently be less than or about 50%, less than or about 30%, of about 5 to 50% or from about 5 to about 30%.

The silica-based composite (or supported chromium catalyst) may be of any suitable particle size, as will be appreciated by those skilled in the art. Illustrative and non-limiting ranges of mean particle size (d50) of the silica (or supported chromium catalyst) composite particles may include from about 10 to about 500 microns, from about 25 to about 250 microns, from about 40 to about 160 microns, or from about 40 to about 120 microns.

POLYMERIZATION METHODS

The supported chromium catalysts of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like. One such olefin polymerization process may involve contacting any supported (activated) chromium catalyst described herein (e.g., prepared by any method described herein) and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor. system under polymerization conditions to produce an olefin polymer.

The catalyst compositions and/or polymerization processes described herein can often use a co-catalyst. In some aspects, the cocatalyst may comprise a metal hydrocarbyl compound, examples of which include non-halogen metal hydrocarbyl compounds, metal halide hydrocarbyl compounds, non-halogen metal alkyl compounds, metal alkyl halide compounds, and so on, in which the metal may be any suitable metal, often metal 13 groups. Therefore, according to certain aspects of the present invention, the metal may be boron or aluminum, while the co-catalyst may contain boron hydrocarbyl or alkyl, or aluminum hydrocarbyl or alkyl, as well as combinations thereof.

In one aspect, the cocatalyst may include an aluminoxane compound, an organoaluminum compound, or an organoboron compound, wherein such cocatalyst comprises combinations of more than one cocatalyst compound. Типичные и неограничивающие примеры алюминоксанов включают метилалюминоксан, модифицированный метилалюминоксан, этилалюминоксан, н-пропилалюминоксан, изопропилалюминоксан, н-бутилалюминоксан, трет-бутилалюминоксан, втор-бутилалюминоксан, изобутилалюминоксан, 1-пентилалюминоксан, 2-пентилалюминоксан, 3-пентилалюминоксан, изопентилалюминоксан, неопентилалюминоксан и т .P. or any combination of them. Representative and non-limiting examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like. or any combination of them.

Typical and non-limiting examples of organoboron compounds include tri-n-butylborane, tripropylborane, triethylborane, and the like. or any combination of them. The cocatalysts that can be used in the catalyst compositions of the present invention are not limited to the cocatalysts described above. Other suitable cocatalysts (such as organomagnesium and organolithium compounds) are well known to those skilled in the art, including, for example, the catalysts described in US Pat. 8114946 and 8309485, which are incorporated herein by reference in their entirety.

Unsaturated monomers that can be used with the catalyst compositions and polymerization processes of the present invention can generally include olefinic compounds having from 2 to 30 carbon atoms per molecule and at least one olefinic double bond. The present invention includes homopolymerization processes using a single olefin, such as ethylene or propylene, as well as copolymerization, terpolymerization, and the like. using an olefin monomer with at least one other olefin compound. For example, the resulting ethylene copolymers, terpolymers, etc. may generally contain a large amount of ethylene (>50 mole percent) and a small amount of comonomer (<50 mole percent), although this is not a requirement. The comonomers that can be copolymerized with ethylene can often contain from 3 to 20 carbon atoms or from 3 to 10 carbon atoms in their molecular chain.

According to the present invention, acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of the present invention may include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene , 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3 -heptene, four normal octenes (eg 1-octene), four normal nonenes, five normal decenes, and the like. or mixtures of two or more of the listed compounds. Cyclic and bicyclic olefins, including but not limited to cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described herein. In addition, according to the present invention, styrene can be used as a monomer. In one aspect, the olefin monomer may include a C ₂ -C ₂₀ olefin; alternatively, C ₂ -C ₂₀ alpha-olefin; alternatively C ₂ -C ₁₀ olefin; alternatively, C ₂ -C ₁₀ alpha-olefin; alternatively, the olefin monomer may include ethylene; or alternatively, the olefin monomer may include propylene.

If a copolymer (or alternatively a terpolymer) is desired, the olefin monomer and olefin comonomer may independently include, for example, a C ₂ -C ₂₀ alpha olefin. In some aspects, the olefin monomer may include ethylene or propylene that is copolymerized with at least one comonomer (eg, C ₂ -C ₂₀ alpha olefin, C ₃ -C ₂₀ alpha olefin, etc.). According to one aspect of the present invention, the olefin monomer used in the polymerization process may include ethylene. In such an aspect, examples of suitable olefin comonomers may include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene , 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, etc. P. or their combinations. According to another aspect of the present invention, the olefin monomer may include ethylene, and the comonomer may include a C ₃ -C ₁₀ alpha olefin; alternatively, the comonomer may include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may include 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may include 1-butene; alternatively, the comonomer may include 1-hexene; or alternatively the comonomer may include 1-octene.

In general, the amount of comonomer introduced into the polymerization reactor system to form the copolymer may be from about 0.01 to about 50 weight percent, based on the combined weight of monomer and comonomer. According to another aspect of the present invention, the amount of comonomer introduced into the polymerization reactor system may be from about 0.01 to about 40 weight percent based on the total weight of monomer and comonomer, or alternatively from about 0.1 to about 35 weight percent. comonomer or from about 0.5 to about 20% of the mass. comonomer.

Without intending to be bound by such a theory, when branched, substituted, or functionalized olefins are used as reactants, it is believed that steric hindrance may interfere with and/or slow down the polymerization process. Thus, branched and/or cyclic olefin moiety(s) further away from the carbon-carbon double bond would not be expected to interfere with the reaction in the same way that the same olefinic substituents closer to the carbon double bond might. -carbon.

According to one aspect of the present invention, at least one monomer/reagent may be ethylene (or propylene), so the polymerization reaction may be a homopolymerization involving only ethylene (or propylene), or a copolymerization with another acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted olefin. In addition, the catalyst compositions of the present invention can be used in the polymerization of diolefin compounds, including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

The supported chromium catalysts described herein have excellent catalytic activity and performance. Typical catalyst productivity is from about 500 to about 5000 grams of polymer per gram of supported chromium catalyst (g/g), from about 800 to about 4000 g/g, or from about 1000 to about 3000 g/g, and the like.

The supported chromium catalysts of the present invention are suitable for any olefin polymerization process using various types of polymerization reactor systems and reactors. The polymerization reactor system may include any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more comonomers) to produce homopolymers, copolymers, terpolymers, and the like. Various types of reactors include reactors that can be called a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, and the like, or combinations thereof. The polymerization conditions for various types of reactors are well known to those skilled in the art. Gas phase reactors may include fluidized bed reactors or multi-stage horizontal reactors. Slurry reactors may contain vertical or horizontal loops. High pressure reactors may include autoclave or tubular reactors. Typically, these types of reactors can operate continuously. In continuous processes, intermittent or continuous discharge of the polymer product may be used. Polymerization reactor systems and processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer and/or diluent.

The polymerization reactor systems of the present invention may comprise one type of reactor in the system, or multiple reactors of the same or different types (eg, single reactor, double reactor, more than two reactors). For example, the polymerization reactor system may include a solution reactor, a gas phase reactor, a slurry reactor, or a combination of two or more of these reactors. The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors connected to each other by means of a transfer device that allows the resulting polymer to be transferred from the first polymerization reactor to the second reactor. The polymerization conditions in one of the reactors may differ from the operating conditions in the other reactor(s). Alternatively, multi-reactor polymerization may involve manual transfer of polymer from one reactor to subsequent reactors to continue polymerization. Multiple reactor systems may include any combination, including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors with loop and/or gas phase reactors. Several reactors may be operated in series or in parallel or/and in series and in parallel. Accordingly, the present invention includes polymerization reactor systems containing one reactor, containing two reactors, and containing more than two reactors. According to some aspects of the present invention, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, as well as multi-reactor combinations thereof.

According to one aspect, the polymerization reactor system may comprise at least one slurry loop reactor, for example, containing vertical or horizontal loops. The monomer, diluent, catalyst and optional comonomer can be continuously fed into the loop reactor in which the polymerization takes place. In general, continuous processes may include continuously introducing monomer/comonomer, catalyst and diluent into a polymerization reactor and continuously withdrawing from such reactor a slurry containing polymer particles and diluent. The reactor effluent may be flashed to remove solid polymer from liquids containing diluent, monomer and/or comonomer. Various technologies can be used to carry out this separation step, including, but not limited to, flash evaporation, which can include any combination of heat and pressure reduction, separation by cyclonic action in either a cyclone or a hydrocyclone, or separation by centrifugation.

An exemplary slurry polymerization process (also known as a particulate process) is described, for example, in US Pat.

Suitable diluents for use in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop reactor polymerization reactions can take place under high volume conditions that do not use a diluent, such as conditions that can be used in the bulk polymerization of propylene to form polypropylene homopolymers.

According to another aspect, the polymerization reactor system may comprise at least one gas phase reactor (eg, a fluidized bed reactor). Such reactor systems may use a continuous recycle stream containing one or more monomers circulating continuously through a fluidized bed in the presence of a catalyst under polymerization conditions. The recycle stream can be removed from the fluidized bed and returned back to the reactor. Simultaneously, the polymer product can be removed from the reactor and new or fresh monomer added to replace the polymerized monomer. Such gas phase reactors may include a multistage gas phase olefin polymerization process wherein olefins are gas phase polymerized in at least two independent gas phase polymerization zones while simultaneously feeding the catalyst-containing polymer produced in the first polymerization zone to the second polymerization zone. One type of gas phase reactor is described in US Pat. Nos. 5,352,749; 4,588,790; 5,436,304;

According to another aspect, the polymerization reactor system may include a high pressure polymerization reactor, for example, may include a tubular reactor or an autoclave reactor. Tubular reactors may have multiple zones to which fresh monomer, initiators or catalysts are added. The monomer can be entrained in an inert gas flow and introduced into one of the zones of the reactor. The initiators, catalysts and/or catalyst components can be entrained in the gas stream and introduced into another zone of the reactor. For polymerization, the gas streams can be stirred. Heat and pressure can be used appropriately in such high pressure polymerization reactors to ensure optimal polymerization reaction conditions.

In yet another aspect, the polymerization reactor system may comprise a solution polymerization reactor in which the monomer/comonomer can be brought into contact with the catalyst composition by suitable agitation or other means. A carrier containing an inert organic diluent or an excess of monomer may be used. If desired, the monomer/comonomer can be brought into contact in the vapor phase with the catalytic reaction product in the presence or absence of liquid material. The polymerization zone can be maintained at a temperature (eg 150°C to 180°C) and pressure which will result in a solution of the polymer in the reaction medium. Stirring can be used to provide better temperature control and maintain uniformity of polymerization mixtures throughout the polymerization zone. Suitable means are used to remove the exothermic heat of polymerization.

In some aspects, the polymerization reactor system may include any combination of a feedstock supply system, a catalyst supply system and/or catalyst components, and/or a polymer recovery system, including a continuous system. In other aspects, suitable reactor systems may include feed purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, offloading, laboratory analysis, and process control.

Polymerization conditions that can be monitored, adjusted and/or controlled to increase efficiency and provide desired polymer properties may include, but are not limited to, reactor temperature, reactor pressure, catalyst system flow rate to the reactor, monomer (and comonomer , when used) to the reactor, monomer concentration in the reactor, olefin polymer yield rate, recycle rate, hydrogen flow rate (when used), reactor cooling state, and the like. The polymerization temperature can affect catalyst performance, polymer molecular weight and molecular weight distribution. A suitable polymerization temperature may be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically, this temperature is from about 60°C to about 280°C, for example, from about 60°C to about 185°C, from about 60°C to about 120°C, or from about 130°C to about 180°C. C depending on the type of polymerization reactor, grade of polymer, etc. In some reactor systems, the temperature of the polymerization reactor may generally be from about 70°C to about 110°C, or from about 125°C to about 175°C. Various polymerization conditions can be maintained substantially constant, for example, to obtain a certain grade of olefin polymer.

Suitable pressures will also vary depending on the type of reactor and polymerization. The pressure for conducting liquid phase polymerization in a loop reactor can typically be less than 1000 psig (6.9 MPa). The pressure for carrying out gas phase polymerization, as a rule, can be from 200 to 500 psig (from 1.4 MPa to 3.4 MPa). High pressure polymerization in tubular or autoclave reactors can generally be carried out at pressures from about 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also operate in the supercritical region typically occurring at higher temperatures and pressures (eg, above 92° C. and 700 psig (4.83 MPa)). Operating at conditions above the critical point in the pressure/temperature diagram (supercritical phase) can provide advantages to such a polymerization reaction method.

Aspects of the present invention also relate to olefin polymerization processes carried out in the absence of added hydrogen. The process for polymerizing olefins according to the present invention may include contacting a supported chromium catalyst and an optional co-catalyst with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer, such polymerization process being carried out in the absence of added hydrogen (in a polymerization reactor). reactor system do not add hydrogen). One skilled in the art will appreciate that hydrogen can be generated in situ using certain catalyst systems in various olefin polymerization processes, and the amount generated may vary depending on the particular catalyst components used, the type of polymerization process used, the polymerization reaction conditions used, etc. .d.

According to other aspects, it may be desirable to carry out the polymerization process in the presence of a certain amount of added hydrogen. Accordingly, the olefin polymerization process of the present invention may include contacting a supported chromium catalyst and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer, such polymerization process being carried out in the presence of added hydrogen ( hydrogen is added to the polymerization reactor system). For example, the ratio of hydrogen to olefin monomer can be controlled in the polymerization process, often by the ratio of hydrogen feed to olefin monomer entering the reactor. The amount of hydrogen added to this process (based on the amount of olefin monomer) can be controlled at a molar percentage concentration generally from about 0.05 to about 20 mol. %, from about 0.1 to about 15 mol. %, from about 0.25 to about 10 mol. % or from about 0.5 to about 10 mol. %. According to some aspects of the present invention, for a particular polymer grade, the ratio of hydrogen in the feed or reactant to olefin monomer can be kept substantially constant during the polymerization cycle. That is, you can choose a particular value for the ratio of hydrogen:olefin monomer and maintain the specified ratio during the polymerization cycle in the range of about +/- 25%. In addition, for a given polymer grade, the addition of comonomer (or comonomers) can be, and usually is, substantially constant throughout the polymerization cycle.

However, in other aspects, it is contemplated that the monomer, comonomer (or comonomers), and/or hydrogen may be intermittently fed into the reactor in an intermittent manner, for example, in a manner similar to that used in US Patent No. 5,739,220 and US Patent Publication No. which are incorporated herein by reference in their entirety.

The concentration of reactants entering the polymerization reactor system can be controlled in such a way as to obtain resins with certain physical and mechanical properties. The intended end use product to be made from the polymer resin and the method for making such a product may ultimately determine the desired properties and characteristics of the polymer. Mechanical properties include testing for tensile strength, bending, impact strength, creep, stress relaxation and hardness. Physical properties include measurements of density, molecular weight, molecular weight distribution, melting point, glass transition temperature, crystallization temperature, density, stereoregularity, cracking, long chain branching, and rheological measurements.

The present invention also relates to polymers obtained using any of the polymerization methods described herein, and includes these polymers. Products of industrial production can be made from polymers obtained according to the present invention, and/or may contain them.

POLYMERS AND PRODUCTS

The olefin polymers included in the present invention may be any polymer derived from any of the olefin monomer and optional comonomer(s) described herein. For example, the olefin polymer may include ethylene homopolymer, ethylene copolymer (e.g., ethylene/α-olefin, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), propylene homopolymer, propylene copolymer, ethylene terpolymer, propylene terpolymer, and the like, including any combination thereof. In one aspect, the olefin polymer may be an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer, while in another aspect, the olefin polymer is an ethylene/1-hexene copolymer.

If the resulting polymer obtained according to the present invention is, for example, an ethylene polymer, its properties can be characterized by various analytical methods known and used in the polyolefin industry. Industrial articles may be made from and/or contain olefin polymers (eg, ethylene polymers) of the present invention, with typical properties of said polymers being summarized below.

Ethylene polymers prepared according to the present invention may have a High Load Melt Flow Index (HLMI) less than or equal to about 100, less than or equal to about 75, or less than or equal to about 50 g/10 min. Suitable HLMI ranges may include, but are not limited to, 0 to about 100, about 1 to about 80, about 1 to about 50, about 1 to about 40, about 1 to about 20, about 2 to about 80, about 2 to about 50, or about 2 to about 40 g/10 min.

The density of ethylene-based polymers made using supported chromium catalysts and the methods described herein is often greater than or equal to about 0.89 g/cm ³ . According to one aspect of the present invention, the density of the ethylene polymer may be from about 0.90 to about 0.97 g/cm ³ . However, in another aspect, the density may be from about 0.91 to about 0.96 g/cm ³ , for example, from about 0.92 to about 0.96 g/cm ³ , from about 0.93 to about 0.955 g/cm ³ , or from about 0.94 to about 0.955 g/cm ³ .

In one aspect, the ethylene polymers described herein may have a Mw/Mn ratio or polydispersity ratio ranging from about 5 to about 40, from about 7 to about 25, or from about 8 to about 18. Additionally or alternatively, the Mz/Mw ratio may be from about 5 to about 10, from about 5 to about 9, or from about 6 to about 8. Without limitation, the ethylene polymer often has a Mw in the range of from about 150 to about 500 kg/mol, from about 200 to about 400 kg/mol or from about 180 to about 350 kg/mol.

In one aspect, the ethylene polymers described herein may have an I ₂₁ /I ₁₀ ratio ranging from about 2 to about 12, from about 3 to about 12, from about 3 to about 10, from about 4 to about 10, or from about 4.5 to about 9. Additionally or alternatively, the CY-a parameter of the ethylene polymer can be from about 0.1 to about 0.3, from about 0.12 to about 0.28, or from about 0.15 to about 0, 25.

Ethylene polymers, be they homopolymers, copolymers, etc., can be molded into a variety of industrial products. Articles that may contain the polymers of the present invention include, but are not limited to, agricultural film, automobile part, bottle, drum, fiber or fabric, food packaging film or container, food service product, fuel tank, geomembrane, household container, lining material, molded article, medical device or material, tube, sheet or tape, toy, and the like. For the manufacture of these products, you can use various methods. Non-limiting examples of such methods include injection molding, blow molding, spin molding, film extrusion, sheet extrusion, shaped extrusion, thermoforming, and the like. In addition, additives and modifiers are often added to these polymers to provide efficient processing of the polymer or beneficial properties of the final product. Such methods and materials are described in the Modern Plastics Encyclopedia , Mid-November 1995 Issue, Vol. 72, no. 12; and Film Extrusion Manual - Process, Materials, Properties , TAPPI Press, 1992; the descriptions of which are incorporated herein by reference in their entirety.

In addition, the present document provides a method for molding or manufacturing an article of industrial production containing a polymer obtained by any of the polymerization methods described herein. For example, the method may include (i) contacting a supported chromium catalyst (eg, prepared as described herein) and an optional co-catalyst with an olefin monomer and an optional olefin comonomer under polymerization conditions in a polymerization reactor system to form an olefin polymer; and (ii) molding an article of industrial production containing an olefin polymer (eg, having any of the properties of the polymers described herein). The molding step may include mixing, melt spinning, extrusion, casting or thermoforming, and the like, including combinations thereof.

EXAMPLES

Further, the present invention is illustrated by the following examples, which should in no way be construed as limiting the scope of the present invention. Upon reading the description provided herein, one skilled in the art will be able to suggest various other aspects, modifications, and equivalents without departing from the spirit of the present invention or the scope of the appended claims.

Melt flow index (MI, g/10 min) was determined according to ASTM D1238 at 190°C with a load of 2.16 kg, I ₁₀ (g/10 min) was determined according to ASTM D1238 at 190°C with a load of 10 kg, and the flow index melt at high load (HLMI, I ₂₁ , g/10 min) was determined according to ASTM D1238 at 190°C with a load of 21.6 kg.

Bulk density was determined according to ASTM D1895 using a 100 ml graduated cylinder.

Molecular weights and molecular weight distributions were obtained on a Waters 150 CV Plus or Polymer Labs PL220 gel permeation chromatograph using trichlorobenzene as solvent at a flow rate of 1 ml/min at 140°C. BHT (butylhydroxytoluene) was used as a stabilizer in a solvent at a concentration of 0.5 g/l. A sample volume of 220 μl was used at a nominal polymer concentration of 6.5 mg/3.5 ml (at room temperature). The column set consisted of two Waters Styragel HT 6E mixed bed columns or three or four PLGel Mixed A columns plus a guard column. An integral broad molecular weight distribution universal calibration method based on high density polyethylene (HDPE) resin, MARLEX® BHB 5003, from Chevron Phillips Chemical Company was used as a broad molecular weight distribution linear polyethylene standard. The parameter values used in the Mark-Huvink equation ([η]= K·M ^a ) for polyethylene were K=39.5 (10 ^-3 ) ml/g and a =0.726. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z-average molecular weight.

The viscosity test specimens were compression molded at 182° C. for a total of three minutes. The samples were allowed to melt at relatively low pressure for one minute and then subjected to high molding pressure for an additional two minutes. Next, the molded specimens were quenched in a cold (room temperature) press. After that, disks with a diameter of 2 mm × 25.4 mm were stamped from the molded blanks to determine the rheological characteristics. Loose samples stabilized with 0.1% of the mass. BHT dispersed in acetone and then dried under vacuum before molding.

Small strain vibrational shear measurements were made at 190°C on a Rheometrics Inc. rheometer. RMS-800 or ARES using parallel plate geometry in the angular frequency range from 0.03 to 100 rad/s. To minimize degradation of the polymers, a nitrogen atmosphere was created in the test chamber of the rheometer. The rheometer was preheated to the initial temperature of the study. After loading the sample and achieving thermal equilibrium in the furnace, the samples were clamped between the plates until a thickness of 1.6 mm was reached and the excess was cut off. A total of approximately 8 minutes elapsed between the time the sample was placed between the plates and the time the frequency sweep began.

In general, the strain values were kept constant during the frequency sweep, but higher strain values were used for low viscosity samples to maintain a measurable torque. When testing high viscosity samples, lower strain levels were used to avoid overloading the torque transducer and to meet the linear viscoelasticity limits of the sample. If necessary, the device automatically reduced the deformation at high frequencies to prevent overloading the torque sensor. Then the data were substituted into the curve of the complex viscosity |η * | on frequency (ω) using a modified three-parameter empirical Carro-Yasuda (CY) model to obtain the zero shear viscosity - η ₀ , the characteristic viscous relaxation time - τ _η and the rheological width parameter - a (parameter CY-a). A simplified empirical Carro-Yasuda (CY) model is presented as follows.

where: | η* ( ω ) | = magnitude of complex shear viscosity;

η ₀ = zero shear viscosity;

τ _η = viscous relaxation time (Tau (η));

a = parameter "rheological width" (parameter CY-a);

n =adjusts the final slope of the exponential function, setpoint 2/11; And

ω = angular frequency of deformation in vibrational shear.

A detailed description of the significance and explanation of the CY model and the parameters derived from it can be found in: CA Hieber and HH Chiang, Rheol. Acta , 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. sci. , 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics , 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.

To characterize the silica-supported catalyst composite, approximately 0.2 g of sample was degassed in a physical adsorption tube using a Micromeritics SmartVacPrep. To prevent some of the fine particles from boiling up in the section of the sampling tube that was not in the heating zone, the pressure was gradually lowered and the temperature was increased abruptly. The pressure was first lowered from ambient pressure to 5 mm Hg. Art. (approximately 667 Pa) with a controlled speed of 5 mmHg. st./s (approximately 667 Pa/s), while keeping the samples at a temperature of 30 °C. After a sufficient vacuum (~0.09 mmHg (about 12 Pa)) was reached, the temperature was raised to 50°C, then to 70°C, then to 90°C, with each temperature jump held for 30 minutes. In the last stage, the temperature was maintained at 300°C for 12 hours, while the final vacuum reached a pressure of about 1 millitorr (0.133 Pa). After cooling to ambient temperature, the samples were placed under a nitrogen atmosphere and analyzed on a Micromeritics TriStar II nitrogen physical adsorption instrument. Approximately 64 adsorption points were obtained to plot the isotherm, and the software packages included with the instrument were used to determine surface areas, total pore volume, and plot pore size distribution curves. The surface area was determined using the BET method (Brunauer, J. Am Chem. Soc. , 1938, 60, 309) using adsorption isotherm points having a P/Po value between 0.0 and 0.2. Pore volume values were calculated based on the isotherm point with the P/Po value closest to 0.982. The pore size distribution was obtained from the desorption isotherm parameters using the Barret-Joyner-Halenda method ( J. Am. Chem. Soc. , 1951, 73, 373), while the thickness curves were obtained using the Halsey equation ( J. Chem. Phys. , 1948, 16, 931). These references are incorporated herein by reference in their entirety.

Absolute pore volumes and surface area values, determined as a function of pore size, were normalized to correspond to the total total pore volume and total BET specific surface area, which were determined from nitrogen sorption.

EXAMPLE 1

Silica Composites Produced from Highly Dispersed Silica and Colloidal Silica

Colloidal silica solution was obtained from WR Grace under the trade name Ludox ^® (Ludox) SM-AS. This solution contained ~25% wt. particles of colloidal silicon dioxide with a diameter of about 5 nm, while gelling and drying in the specified solution, silicon dioxide is formed with a nominal specific surface according to the BET method of 300 m ² /g. The colloidal solution of silica was stabilized by adding small amounts of ammonium hydroxide, and therefore, upon receipt, the specified solution was in an alkaline state. This colloidal solution was used as component II of silicon dioxide ("adhesive" component) to obtain a number of composites based on silicon dioxide.

Silica component I was obtained from Cabot Corp. under the name Cabosil ^® (Cabosil) S17D. It had a very loose feather-like structure and is described as a non-porous material obtained by flame hydrolysis, that is, as "highly dispersed" silicon dioxide. Highly dispersed silicas were examined using electron microphotography so that the average size ratio was about 5:1 (see, for example, Fig. 2 in Forsman et al., Can. J. Phys. 65, 767 (1987), in full incorporated herein by reference). Silica component I has been used as the "frame structure" or "frame" component of silica composites.

The highly dispersed silica component I was first suspended in sufficient water to form a wet component in the liquid, although suitable silica components I can also be supplied "wet" in liquid dispersions with a solids content of ~20 wt%. Typically, Example 1 required about 10 ml of water to suspend each gram of highly dispersed silica. The colloidal silica component II ("glue" silica Ludox ^® (Ludox)) was then added to form the supported polymerization catalyst, and titanium and chromium components were added in some subsequent examples. Titanium was added with ^Tyzor® (Tizor) TE, a triethanolamine titanate complex obtained from Dorf Ketal (being alkaline, it was compatible with the ^Ludox® component). Chromium (III) acetate was used as a source of chromium. After all of the silica components (and transition metal components, if applicable) were combined to form a slurry, the pH was adjusted to neutral by dropwise addition of acetic acid. Typically, such a suspension gelled or at least thickened upon reaching pH 7. The resulting gel was then dried overnight in a vacuum oven at a set temperature of 100°C. This procedure was used to prepare the silica composites shown in Tables I-IV and in FIGS. 1-7 .

In some experiments, the suspension was simply left to stand until it gelled. For example, one of the samples that used 100% colloidal silicon dioxide Ludox ^® (Ludox) (without highly dispersed silicon dioxide), after adding the titanium and chromium components, was left to settle at room temperature, while after a few days the specified sample spontaneously formed a gel.

And in several other experiments, colloidal silicon dioxide Ludox ^® (Ludox) was quickly added to the acid solution to quickly convert the suspension from a base-stabilized solution to an acid-stabilized solution. Oxalic acid was dissolved in water as the acid component, which could then be used to dissolve the freshly precipitated titanium dioxide. When an amine was added to neutralize the oxalic acid, gelation occurred, this time as a result of exposure to an acidic pH.

In FIG. 1-7 show the distribution of pore volume versus pore diameter (nm) for colloidal silica (component II silica), fumed silica (component I silica), and silica composites prepared from two silica components (t e. colloidal silicon dioxide and highly dispersed silicon dioxide). These figures unexpectedly demonstrated the influence of the relative amount of colloidal silicon dioxide used on the pore volume distribution. The aim of these experiments was to obtain a large number of mesopores (generally 10 to 100 nm in diameter and in particular 30 to 100 nm) with a minimum number of small pores (less than 10 nm in diameter and in particular less than 5 nm in diameter, and especially less than 3 nm). Very large pores (often over 100 nm) are also not particularly useful as they can contribute to dusting during handling (because they are usually a low bulk density powder). As shown in FIG. 1-7 , silica composites were unexpectedly found with maximum pore diameters of more than 10 nm with a content of silicon dioxide component II (the colloidal "glue" component of silicon dioxide) of less than 25% of the mass. of the total amount of silicon dioxide, while the number of mesopores (typically 10 to 100 nm in diameter and, in particular, from 30 to 100 nm) was even higher when the content of component II of silicon dioxide in the range from 5 to 15 wt%.

Some of the data presented graphically in FIG. 1-7 are summarized in tables I-IV . Table I shows the result of summing pore volume over several pore size categories using dV/dLogD values obtained from nitrogen desorption curves. Table I also lists the total pore volume, BET surface area, and bulk density of the silica components and silica composites. Table II shows the same pore volume distribution, but expressed in absolute terms (ml/g). Similar data for surface areas as a function of pore diameter are given in Table III and Table IV using dS/dlogD. Since catalyst activity is proportional to surface area, the relative contribution of different pore sizes to the overall catalyst activity can be determined. These tables also contain a column (25+Ti) for a composite based on silicon dioxide obtained using 25% of the mass. colloidal silica to which titanium was added prior to the formation of the composite (silica-titanium dioxide) - see the description of example 3A below. After drying and sieving said silica composite (containing titanium), part of it was calcined in air at 500° C. and analyzed in the same manner as the other silica composites shown in the tables and figures.

As shown in these tables and figures, silica composites were obtained with a bulk density in the range from 0.1 to 0.35 g/ml, a total pore volume in the range from 0.4 to 1.2 ml/g, specific surface according to the BET method in the range from 290 to 360 m ² /g, the maximum pore diameter in the range from 9 to 30 nm and the average pore diameter in the range from 8 to 13 nm. In addition, in some of these silica composites, the percentage of total pore volume in pores with diameters in the range from 10 to 50 nm (or in the range from 10 to 100 nm) was also from 28 to 72%, the percentage of total volume pores in pores with diameters in the range from 30 to 100 nm ranged from 1 to 4%, the percentage of the total pore volume in pores with diameters less than or equal to 5 nm ranged from 7 to 13%, the volume of pores with diameters in the range of 10 up to 50 nm (or in the range from 10 to 100 nm) was from 0.2 to 0.9 ml / g, the percentage of the total surface area in pores with diameters in the range from 10 to 50 nm (or from 10 to 100 nm) ranged from 18 to 47%, the percentage of surface area in pores with diameters less than or equal to 5 nm ranged from 18 to 28%, and the surface area of pores with diameters in the range from 10 to 50 nm (or in the range from 10 to 100 nm ) ranged from 58 to 170 m ² /g.

It is important to note the unexpectedly high maximum pore diameters when the content of component II of silicon dioxide (colloidal silicon dioxide) in the range from 5 to 15% of the mass. and furthermore, a total pore volume that is much higher than either of the two silica components.

EXAMPLE 2

Silica Composites Produced from Highly Dispersed Silica and Silicate Oligomer

In Example 2, silica component I was obtained from Evonik Corp. called Aerosil ^® (Aerosil) 380 ("fine" silicon dioxide). The silica component II (the "adhesive" component) was hydrolyzed ethyl polysilicate, available from Evonik as ^Silbond® 40. It is a condensed ethyl polysilicate with an average molecular weight of about 800.

First, 20 g of Aerosil ^® (Aerosil) 380 was added to 100 ml of isopropanol, 30 ml of water and 10 ml of concentrated NH ₄ OH. The suspension was intensively stirred for several minutes, and then Silbond ^® (Silbond) 40 was quickly added. subjected to hydrolysis and gelation, embedding Aerosil ^® (Aerosil) in the overall structure. The resulting gel was then washed once with water and dried. After calcination at 400° C., the final silica composites were obtained as shown in Tables V-VIII and in FIGS. 8-11 .

In example 2, gelation occurred with the help of a base. However, another way to obtain such composites may be to combine Aerosil ^® (Aerosil) in an acidic suspension (which uses, for example, oxalic acid as an acidic component) and optionally chromium and/or titanium components. Further, an alcohol solution of Silbond ^® (Silbond) 40 can be added to an acidic solution, which hydrolyzes Silbond ^® (Silbond) to obtain very fine "glue" particles, usually small enough to provide a surface area of 500 to 1000 m ² /g due to one component Silbond ^® (Silbond) 40. Next cause gelation by neutralizing the acid by adding ammonia or amine.

In FIG. 8-11 shows the distribution of pore volume as a function of pore diameter (nm) for Silbond ^® silica (Silbond) (component II of silicon dioxide), highly dispersed silica Aerosil ^® (Aerosil) (component I of silicon dioxide) and composites based on silicon dioxide obtained from two components of silicon dioxide (ie silicon dioxide Silbond ^® (Silbond) and highly dispersed silicon dioxide). These figures unexpectedly demonstrated the influence of the relative amount of silica Silbond ^® (Silbond) used on the distribution of pore volume. As shown in FIG. 8-11 , silica-based composites with a maximum pore diameter of more than 10 nm were unexpectedly found with a content of silicon dioxide component II ("adhesive" silica component Silbond ^® (Silbond)) from 25 to 80% of the mass. of the total amount of silicon dioxide, while the number of mesopores (typically 10 to 100 nm in diameter, and in particular 30 to 100 nm) was very high when the content of component II of silicon dioxide was 25 wt%.

Some of the data presented graphically in FIG. 8-11 are summarized in tables V-VIII . Table V shows the result of summing pore volume over several pore size categories using dV/dLogD values obtained from nitrogen desorption curves. Table V also shows the total pore volume, BET surface area, and bulk density of the silica components and silica composites. Table VI shows the same pore volume distribution, but expressed in absolute terms (ml/g). Similar data for surface areas versus pore diameter are summarized in Table VII and Table VIII using dS/dlogD. Since catalyst activity is proportional to surface area, the relative contribution of different pore sizes to the overall catalyst activity can be determined.

As shown in the tables and figures, silica composites were obtained with a bulk density in the range of 0.25 to 0.31 g/ml, a total pore volume in the range of 0.5 to 1.3 ml/g, specific surface area according to the BET method in the range from 190 to 240 m ² /g, the maximum pore diameter in the range from 18 to 38 nm and the average pore diameter in the range from 10 to 24 nm. In addition, in some of these silica composites, the percentage of total pore volume in pores with diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm) was also 40 to 85%, the percentage of total volume pores in pores with diameters in the range from 30 to 100 nm ranged from 4 to 30%, the percentage of the total pore volume in pores with diameters less than or equal to 5 nm ranged from 3 to 20%, the volume of pores with diameters in the range of 10 up to 50 nm (or in the range from 10 to 100 nm) was from 0.2 to 1.1 ml/g, the percentage of the total surface area in pores with diameters in the range from 10 to 50 nm (or from 10 to 100 nm) ranged from 20 to 65%, the percentage of surface area in pores with diameters less than or equal to 5 nm ranged from 8 to 42%, and the surface area of pores with diameters in the range from 10 to 50 nm (or in the range from 10 to 100 nm ) ranged from 40 to 140 m ² /g.

It is important to note the unexpectedly high maximum pore diameter, average pore diameter, total pore volume and percentage of total pore volume in pores with diameters in the range from 30 to 100 nm at a content of silica component II (Silbond ^® silicon dioxide (Silbond)) of 25 wt%. .

EXAMPLE 3

Catalyst and polymerization experiments

Catalysts were prepared using the methods described in Examples 1-2, in which the appropriate titanium-containing compounds and chromium-containing compounds were added to the slurry before or after gelation. After drying the chromium catalyst on the support, said catalyst was calcined at 650° C. for three hours and then tested for polymerization activity in a 2.2 liter stainless steel reactor. Isobutane (2 L) was used in all experiments. A small amount of activated chromium catalyst was added through the feed port while the isobutane vapor was slowly removed. The feed opening was closed and isobutane was added. The contents of the reactor were stirred and heated to the required operating temperature of 105°C, and then ethylene (without comonomer, hydrogen, or cocatalyst) was introduced into the reactor. Ethylene was added as needed to maintain reactor pressure of 550 psig (about 3.8 MPa g) for the required duration of each polymerization experiment. Thereafter, the reactor was vented and cooled, and the polymer was recovered.

For example 3A, 15 g of ^Cabosil® (Cabosil) S17D (410 m ² /g of highly dispersed silica from Cabot Corp) was used as component I of silicon dioxide, and 5 g of silica of Ludox ^® (Ludox) was used as component of silicon dioxide. SM-AS (20 g 25% suspension). Both components were added to 50 ml of water in which 5.3 g of ^Tyzor® (Tizor) TE (triethanolamine titanate) was dissolved. The initially formed paste was mixed and kneaded by hand for about 15 minutes, as a result of which it turned into a thick liquid. The resulting liquid was left overnight, which led to its transformation into a gel. This gel was then dried for 12 hours in a vacuum oven, the temperature of which was set at 100°C.

As a result, hard lumps were formed, which were then ground into powder, passing through a sieve with a mesh size of 35 mesh. Then about 10 g of the obtained dry powder of silicon dioxide-titanium dioxide (~3.5 wt. % titanium) was placed in an activator quartz tube together with 0.67 g of chromium (III) acetylacetonate powder. The physical mixture was heated in a flow of dry air to 650°C, which led to the sublimation of chromium and its subsequent incorporation into a substrate based on silicon dioxide-titanium dioxide. After three hours of fluidization at 650° C. in dry air, the catalyst was cooled and stored under dry nitrogen. The resulting catalyst had a uniform orange color, indicating that chromium was attached to the support as a hexavalent compound. The catalyst had a BET surface area of 320 m ² /g and a pore volume of 1.04 ml/g.

A sample of this catalyst (0.0995 g) was introduced into the reactor and an ethylene polymerization experiment was performed at 105° C. and 550 psig ethylene pressure for 2 hours. With this catalyst, 160 g of polymer were obtained - a productivity of 1608 g/g. This polymer unexpectedly had a high HLMI of 18.4 compared to an HLMI of 5 that is typically obtained using catalysts made from simple silica gels.

For example 3B, 9 g of ^Cabosil® (Cabosil) S17D was combined with 1 g ^of Ludox® (Ludox) SM-AS (4 ml) and 100 ml of water. The resulting suspension was stirred for 10 minutes until complete mixing of the two components of silicon dioxide. Chromium acetate (0.43 g) was added to the suspension, followed by a few drops of acetic acid to neutralize the ammonia coming from Ludox ^® (Ludox). After the pH became neutral, the slurry thickened considerably and was then left to dry overnight at 25° C. in the open air. As a result, solid lumps of catalyst were obtained, which were crushed and sieved through a sieve with a mesh size of 35 mesh. The BET specific surface area of the obtained catalyst was 347 m ² /g and the pore volume was 1.00 ml/g.

Next, the resulting catalyst was activated in a stream of dry air at 650°C for 2 to 3 hours to obtain an orange catalyst. A small sample of this catalyst (0.1731 g) was then introduced into the reactor and a polymerization experiment was carried out as described above. With this catalyst, 191 g of polymer were obtained after 90 minutes - a productivity of 1103 g/g. The HLMI of the resulting polymer was 6.3, which was surprisingly higher than when commercial Cr/silica catalysts were activated and tested under the same conditions.

For example 3C, in 659 ml of isopropanol, 55 ml of water and 11 ml of concentrated ammonium hydroxide (28% NH ₃ ) were added together with 31 g of Aerosil ^® (Aerosil) 380, then vigorously stirred at maximum speed for 45 minutes to break the Aerosil ^® agglomerates ( Aerosil). Next, 25 ml of ^Silbond® 40 (10.6 g of SiO ₂ ) was added to the resulting mixture. Within 5 minutes ammonia hydrolyzed the ^Silbond® 40 to form a gel, as evidenced by the thickening of the slurry. After standing overnight, the silica was filtered from the suspension and washed with 2 L of water. After the second filtration, the solids were dried in a vacuum oven overnight at 100°C. After being passed through a 35 mesh sieve, the resulting silica composite powder had a BET surface area of 215 m ² /g and a pore volume of 1.27 ml/g.

A 10 g sample of this powder was dry mixed with 0.67 g of chromium (III) acetylacetonate powder and then calcined at 650°C for three hours to obtain an orange powder, indicating addition of chromium and conversion to hexavalent chromium. A small sample of this catalyst (0.1625 g) was then introduced into the reactor and a polymerization experiment was carried out as described above. With this catalyst, 216 g of polymer were obtained after 78 minutes - a productivity of 1329 g/g. The HLMI of the resulting polymer was 2.2.

For Example 3D, 5.51 g of oxalic acid hydrate, 6.65 ml of titanium isopropoxide, 5 ml of 30% H ₂ O ₂ , 5.07 ml of dimethylformamide and 1.16 g of chromium acetate were added to 100 ml of water. After stirring for about 5 minutes, an orange solution was obtained. Next was added 8 g of Ludox ^® (Ludox) SM-AS, and then 30 g of Aerosil ^® (Aerosil) 308 to obtain a suspension. To bring the pH to 7 was added a few milliliters of 28% ammonium hydroxide solution. The resulting suspension thickened, indicating gelling, and this mixture was left to dry at 25°C for three days. Received semi-solid lumps of red color, which are crushed and passed through a sieve with a mesh size of 35 mesh.

Then, the resulting catalyst was calcined as described above in dry air at 650° C. for 3 hours to obtain an orange catalyst. A small sample of this catalyst (0.0708 g) was then introduced into the reactor and a polymerization experiment was carried out as described above. With this catalyst, 193 g of polymer were obtained after 114 minutes - a productivity of 2726 g/g. The HLMI of the resulting polymer was 26.1.

For example 3E, the procedure used to prepare catalyst 3B was repeated, except that 9.5 g of ^Cabosil® (Cabosil) S17D and 0.5 g ^{of Ludox®} (Ludox) SM-AS (2 ml) were used. The BET specific surface area of the silica composite was 359 m ² /g and the pore volume was 1.15 ml/g. After calcination at 650° C. using 0.2254 g of this catalyst, 241 g of polymer was obtained after 102 minutes - a productivity of 1069 g/g. The HLMI of the resulting polymer was 7.1.

For example 3F, a solution was prepared from 335 ml of water, 12.4 g of Tyzor ^® (Tizor) TE (titanium triethanolamine chelate), 1.25 g of chromium acetate and 4.9 g of Ludox ^® (Ludox) SM-AS silicon dioxide (19, 6 ml of Ludox ^® solution (Ludox)). Then was added 30 g of Aerosil ^® (Aerosil) 380 to obtain a suspension. After heating to boiling for 30 min, gelation occurred. After drying overnight in a vacuum oven at 100°C, semi-solid lumps were obtained, which were crushed and passed through a 35 mesh sieve. After calcination at 650° C. using 0.1024 g of this catalyst, 194 g of polymer were obtained after 105 minutes - a productivity of 1895 g/g. The HLMI of the resulting polymer was 19.3.

For Example 3G, a procedure similar to Example 3F was followed. The catalyst was obtained by spray drying a suspension containing 90% of the mass. Aerosil ^® (Aerosil) 380 and 10% of the mass. Ludox ^® (Ludox) SM-AS together with Tyzor ^® (Tizor) TE (corresponding to 3.5% wt. titanium on the final catalyst) and chromium acetate (corresponding to 1% wt. chromium on the final catalyst). A fine catalyst powder was obtained, the productivity of which after calcination at 650°C was 2537 g/g (using 0.041 g of catalyst, 104 g of polyethylene was obtained after 143 minutes). The HLMI of the resulting polymer was 38.6.

Table IX lists some characteristics (surface area, pore volume, average pore diameter, maximum pore diameter) of the silica-based composites and catalysts used in Examples 3A-3G, and various properties of ethylene polymers prepared using the respective catalysts. Table X summarizes the pore volume over several pore size categories using dV/dLogD values obtained from the nitrogen desorption curves for silica composites and catalysts 3A-3C and 3E, this table also includes total pore volume, specific BET surface and maximum and average pore diameter. Table XI shows the same pore volume distribution, but expressed in absolute terms (ml/g). In the presented tables, characteristics in terms of surface area, pore volume, average pore diameter, maximum pore diameter, bulk density, pore size and surface area distribution, etc. refer to composites based on silicon dioxide. No significant change is expected due to the addition of chromium to form a supported catalyst, and therefore it can be expected that substantially the same data in Tables IX-XI as given for the silica composite would apply to the supported catalyst.

As shown in the tables below, silica composites (and hence supported chromium catalysts) have been produced with total pore volume ranging from 1 to 1.3 ml/g, BET specific surface area ranging from 215 to 360 m ² /g, the maximum pore diameter in the range from 17 to 35 nm and the average pore diameter in the range from 11 to 24 nm. In addition, in some of the given silica-based composites, the percentage of total pore volume in pores with diameters in the range from 10 to 50 nm (or in the range from 10 to 100 nm) was also from 50 to 85%, the percentage of the total volume pore volumes in pores with diameters ranging from 30 to 100 nm ranged from 1 to 30%, the percentage of total pore volume in pores with diameters less than or equal to 5 nm ranged from 3 to 11%, and volumes of pores with diameters ranging from 10 to 50 nm (or in the range of 10 to 100 nm) was 0.5 to 1.1 ml/g.

Table I - Example 1

Colloidal silicon dioxide (% mass) 100 65 50 25 15 10 5 0 25+ti Maximum pore diameter (nm) 6.2 6.0 6.7 9.0 26.3 25.8 28.8 25.9 17.3 Average pore diameter (nm) 9.8 5.9 6.7 8.5 11.1 11.5 12.8 7.6 13.0 Total Pore Volume (PV) (ml/g) 0.47 0.48 0.50 0.66 0.94 1.00 1.15 0.71 1.04 BET specific surface (m ² /g) 191 324 296 312 339 347 359 372 320 Bulk density (g/ml) 0.37 0.33 0.31 0.28 0.24 0.21 0.14 0.04 0.27 PV at diameter < 3 nm (%) 1.0 1.4 0.7 0.9 1.9 1.9 1.5 9.1 2.1 PV at 3-5 nm diameter (%) 21.9 30.5 15.3 8.2 10.4 9.1 6.4 19.8 8.1 PV at 5-10 nm diameter (%) 76.4 67.1 82.5 62.2 45.4 39.4 20.2 36.6 26.7 PV at 10-50 nm diameter (%) 0.7 1.0 1.5 28.7 42.1 49.6 71.7 32.7 62.7 PV at 50-100 nm diameter (%) - - - - 0.2 0.1 0.2 1.3 0.4 PV at diameter >100 nm (%) - - - - - - - 0.5 - PV at 30-100 nm diameter (%) - 0.1 - 0.1 2.3 1.0 3.6 4.6 3.2

Table II - Example 1

Colloidal silicon dioxide (% mass) 100 65 50 25 15 10 5 0 25+ti Data in ml/g, based on dV/dlogD Diameter < 3 nm 0.01 0.01 - 0.01 0.02 0.02 0.02 0.06 0.02 Diameter 3-5 nm 0.10 0.14 0.08 0.05 0.10 0.09 0.07 0.14 0.08 Diameter 5-10 nm 0.36 0.32 0.41 0.41 0.43 0.39 0.23 0.26 0.28 Diameter 10-50 nm - 0.01 0.01 0.19 0.40 0.50 0.83 0.23 0.65 Diameter 50-100 nm - - - - - - - 0.01 0.01 Diameter >100 nm - - - - - - - - - Total 0.47 0.48 0.50 0.66 0.94 1.00 1.15 0.71 1.04 Diameter 30-100 nm - - - - 0.02 0.01 0.04 0.03 0.03

Table III - Example 1

Colloidal silicon dioxide (% mass) 100 65 50 25 15 10 5 0 25+ti Diameter >100 nm (%) - - - - - - - - - Diameter 50-100 nm (%) - - - - - - - 0.1 0.1 Diameter 10-50 nm (%) 0.3 0.4 0.7 18.6 22.8 28.7 46.5 13.3 37.8 Diameter 5-10 nm (%) 68.8 58.5 75.3 62.9 49.7 45.1 29.2 31.6 34.2 Diameter 3-5 nm (%) 28.5 37.8 22.1 15.2 20.4 18.9 16.7 29.5 18.8 Diameter < 3 nm (%) 2.4 3.3 1.9 3.3 7.0 7.3 7.6 25.6 9.1 Diameter 30-100 nm (%) - - - - 0.5 0.2 1.1 0.7 0.8

Table IV - Example 1

Colloidal silicon dioxide (% mass) 100 65 50 25 15 10 5 0 25+ti Data in ^m2 /g, based on dS/dlogD Diameter >100 nm - - - - - - - 0.1 - Diameter 50-100 nm - - - - 0.1 0.1 0.1 0.4 0.2 Diameter 10-50 nm 0.6 1.3 2.1 58.0 77.4 99.6 166.8 49.3 121.0 Diameter 5-10 nm 131.3 189.7 222.9 196.4 168.6 156.6 104.9 117.5 109.3 Diameter 3-5 nm 54.5 122.4 65.5 47.3 69.0 65.5 60.0 109.6 60.2 Diameter < 3 nm 4.6 10.6 5.5 10.3 23.9 25.2 27.2 95.1 29.3 Total 191 324 296 312 339 347 359 372 320 Diameter 30-100 nm - - - - 1.7 0.8 3.8 2.4 2.6

Table V - Example 2

Silicon dioxide Silbond ^® (Silbond) (% wt.) 100 80 50 25 0 Maximum pore diameter (nm) 17.8 18.0 37.7 34.5 25.9 Average pore diameter (nm) 14.0 15.1 10.4 23.6 7.6 Total Pore Volume (PV) (ml/g) 0.99 0.89 0.50 1.27 0.71 BET specific surface (m ² /g) 283 235 192 215 372 Bulk density (g/ml) 0.35 0.31 0.28 0.25 0.05 PV at diameter >100 nm (%) - 0.4 0.9 0.3 0.5 PV at 50-100 nm diameter (%) - 1.6 3.6 1.5 1.3 PV at 10-50 nm diameter (%) 72.9 67.2 42.7 82.7 32.7 PV at 5-10 nm diameter (%) 23.3 24.2 32.9 11.9 36.6 PV at 3-5 nm diameter (%) 3.3 5.4 13.5 2.8 19.8 PV at diameter < 3 nm (%) 0.5 1.3 6.3 0.8 9.1 PV at 30-100 nm diameter (%) 0.3 4.9 10.3 29.5 4.6

Table VI - Example 2

Silicon dioxide Silbond ^® (Silbond) (% wt.) 100 80 50 25 0 Data in ml/g, based on dV/dlogD Diameter >100 nm - - - - - Diameter 50-100 nm - 0.01 0.02 0.02 0.01 Diameter 10-50 nm 0.72 0.60 0.21 1.05 0.23 Diameter 5-10 nm 0.23 0.22 0.16 0.15 0.26 Diameter 3-5 nm 0.03 0.05 0.07 0.04 0.14 Diameter < 3 nm - 0.01 0.03 0.01 0.06 Total 0.99 0.89 0.50 1.27 0.71 Diameter 30-100 nm - 0.04 0.05 0.37 0.03

Table VII - Example 2

Silicon dioxide Silbond ^® (Silbond) (% wt.) 100 80 50 25 0 Diameter >100 nm (%) - - 0.1 - - Diameter 50-100 nm (%) - 0.2 0.4 0.4 0.1 Diameter 10-50 nm (%) 55.4 46.4 20.8 64.2 14.2 Diameter 5-10 nm (%) 33.4 33.5 36.2 27.1 33.9 Diameter 3-5 nm (%) 8.7 13.7 26.1 8.2 31.7 Diameter < 3 nm (%) 2.4 6.2 16.4 - 20.0 Diameter 30-100 nm (%) 0.1 1.2 1.8 13.0 0.7

Table VIII - Example 2

Silicon dioxide Silbond ^® (Silbond) (% wt.) 100 80 50 25 0 Data in ^m2 /g, based on dS/dlogD Diameter >100 nm - 0.1 0.1 0.1 0.1 Diameter 50-100 nm - 0.6 0.8 0.8 0.5 Diameter 10-50 nm 156.9 109.0 39.9 138.1 52.9 Diameter 5-10 nm 94.6 78.7 69.6 58.3 126.2 Diameter 3-5 nm 24.7 32.2 50.1 17.7 117.6 Diameter < 3 nm 6.7 14.5 31.5 - 74.5 Total 283 235 192 215 372 Diameter 30-100 nm 0.2 2.7 3.5 28.0 2.6

Table IX - Example 3

Example 3A 3B 3D 3E 3G Silica I ^Cabosil®
(Cabosil) ^Cabosil®
(Cabosil) ^Aerosil®
(Aerosil) ^Aerosil®
(Aerosil) ^Cabosil®
(Cabosil) ^Aerosil®
(Aerosil) Cabosil ^® (Cabosil) Silica II Ludox ^® (Ludox) Ludox ^® (Ludox) Silbond ^® (Silbond) Ludox ^® (Ludox) Ludox ^® (Ludox) Ludox ^® (Ludox) Ludox ^{® (} Ludox) Ratio I:II 75:25 90:10 75:25 80:20 95:5 86:14 90:10 Surface area (m ² /g) 320 347 215 - 359 - - Pore volume (ml/g) 1.04 1.00 1.27 - 1.15 - - Average pore diameter (nm) 13.0 11.5 23.6 - 12.8 - - Maximum pore diameter (nm) 17.3 25.8 34.5 - 28.8 - - Bulk density (g/ml) 0.27 0.21 0.24 - 0.14 - - Productivity (y/y) 1608 1103 1329 2726 1069 1895 2537 MI - I ₂ (g/10 min) 0.09 - - 0.25 - 0.10 0.55 I ₁₀ (g/10 min) 3.5 0.8 - 4.9 1.0 3.3 8.4 HLMI - I ₂₁ (g/10 min) 18.4 6.3 2.2 26.1 7.1 19.3 38.6 I ₂₁ /I ₂ (HLMI/MI) 212 - - 104 - 202 70 I ₂₁ /I ₁₀ 5.2 8.0 - 5.3 7.1 5.8 4.5 Mn (kg/mol) 20 20 24 - 23 - - Mw (kg/mol) 235 253 320 - 231 - - Mz (kg/mol) 1759 1761 2059 - 1527 - - Mw/Mn 11.6 12.7 13.1 - 9.7 - - Mz/Mw 7.5 7.0 6.4 - 6.6 - - η ₀ (MPa-sec) 0.71 2.24 4.95 - 0.92 - - Tau (sec) 2.9 11.3 30.7 - 3.8 - - CY-a 0.18 0.18 0.20 - 0.20 - -

Table X - Example 3

Example 3A 3B 3E Maximum pore diameter (nm) 17.3 25.8 34.5 28.8 Average pore diameter (nm) 13.0 11.5 23.6 12.8 Total Pore Volume (PV) (ml/g) 1.04 1.00 1.27 1.15 BET specific surface (m ² /g) 320 347 215 359 PV at diameter >100 nm (%) - - 0.3 - PV at 50-100 nm diameter (%) 0.4 0.1 1.5 0.2 PV at 10-50 nm diameter (%) 62.7 49.6 82.7 71.7 PV at 5-10 nm diameter (%) 26.7 39.4 11.9 20.2 PV at 3-5 nm diameter (%) 8.1 9.1 2.8 6.4 PV at diameter < 3 nm (%) 2.1 1.9 0.8 1.5 PV at 30-100 nm diameter (%) 3.2 1.0 29.5 3.6

Table XI - Example 3

Example 3A 3B 3E Data in ml/g, based on dV/dlogD Diameter >100 nm - - - - Diameter 50-100 nm - - 0.02 - Diameter 10-50 nm 0.65 0.50 1.05 0.83 Diameter 5-10 nm 0.28 0.39 0.15 0.23 Diameter 3-5 nm 0.08 0.09 0.04 0.07 Diameter < 3 nm 0.02 0.02 0.01 0.02 Total 1.04 1.00 1.27 1.15 Diameter 30-100 nm 0.03 0.01 0.37 0.04

The present invention has been described above with reference to numerous aspects and specific examples. In light of the above detailed description, those skilled in the art will be able to suggest many embodiments of the invention. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following aspects (aspects are described as "comprising" but alternatively may "consist essentially of" or "consist of"):

Aspect 1. A method for producing a composite (composition) based on silicon dioxide, including:

(1) combining component I of silicon dioxide and component II of silicon dioxide in a diluent containing at least about 70% of the mass. water, to obtain a mixture; And

(2) forming in said mixture a (co-thickened) silica composite; wherein:

the silica component I comprises irregular and non-spherical silica particles having an average size ratio of at least about 2:1 and a BET specific surface area ranging from about 150 to about 1000 m ² /g;

the silica component II comprises colloidal silica; And

the silica-based composite is characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 2. The method defined according to aspect 1, in which the diluent contains any suitable amount of water or an amount of water in any range given herein, for example, at least about 80 wt%, at least about 90 wt%, at least about 95% of the mass. etc.

Aspect 3 The method as defined in Aspect 1 or 2 wherein the silica component II comprises ^Ludox® fumed silica, ^Nyacol® fumed silica, Levisil fumed silica, or any combination thereof.

Aspect 4. The method defined according to any one of aspects 1-3, wherein the colloidal silica is characterized by any suitable average aspect ratio or any average aspect ratio provided herein (e.g., less than 1.8:1, less than 1.5: 1, etc.), any suitable average (d50) particle size, or any average (d50) particle size described herein (e.g., about 3 to about 25 nm, about 3 to about 18 nm, etc.). and any suitable BET specific surface area or any BET specific surface area provided herein (e.g., about 200 to about 1000 m ² /g, about 225 to about 500 m ² /g, etc. .d.).

Aspect 5. The method defined according to any one of aspects 1-4, wherein the amount of silica component II, based on the total amount of silica component I and silica component II, is in any suitable range or any range given herein, for example , from about 1 to about 35 wt. -%, from about 2 to about 25 wt. -%, from about 3 to about 20 wt.%. etc.

Aspect 6. The method defined according to any one of aspects 1-5, wherein the formation (co-gelling) in said mixture of a silica composite comprises any suitable method for producing a silica composite or any method described herein, for example, adjusting the pH of the mixture, removing water from the mixture and/or heating the mixture, adding a metal ion to the mixture, adding an organic solvent (eg, alcohol) to the mixture, storing the mixture for a suitable period of time, etc. or any combination of them.

Aspect 7. A method for producing a composite (composition) based on silicon dioxide, including:

(1) combining the silica component I and the silica component II in a solvent to form a mixture; And

(2) forming in said mixture a (co-thickened) silica composite; wherein:

the silica component I comprises irregular and non-spherical silica particles having an average size ratio of at least about 2:1 and a BET specific surface area ranging from about 150 to about 1000 m ² /g;

the silicon dioxide component II includes a silicon compound (silicon-containing compound); And

the silica-based composite is characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 8 The method defined according to aspect 7 wherein the solvent comprises any suitable solvent or any solvent described herein, e.g., a ketone (e.g., acetone), alcohol (e.g., methanol, ethanol, n-propanol, isopropanol, etc.) .d.), glycol, ester, ether, acetonitrile, etc. or any combination of them.

Aspect 9. The method defined according to aspect 7, wherein the solvent contains alcohol and water.

Aspect 10. The method defined according to any one of aspects 7-9, wherein the silicon compound comprises any suitable silicon compound or any silicon compound described herein, e.g., silicon alkoxide (e.g., tetraethylorthosilicate), silicon halide, silicon hydride, silane , hydrocarbylsilane, siloxane, etc. or any combination of them.

Aspect 11 A method as defined in any one of aspects 7-9, wherein the silicon compound comprises sodium silicate, ethyl silicate, a silicate oligomer (eg, an ethyl silicate oligomer), or any combination thereof.

Aspect 12 The method as defined in any one of aspects 7-9 wherein the silicon compound comprises ^Silbond® silicate.

Aspect 13. The method defined according to any one of aspects 7-12, wherein the amount of silica component II, based on the total amount of silica component I and silica component II, is in any suitable range or any range given herein, for example , from about 10 to about 90 wt. -%, from about 15 to about 60 wt. -%, from about 20 to about 80 wt.%. etc.

Aspect 14. The method defined according to any one of aspects 7-13, wherein the formation (co-gelling) in said mixture of a silica composite comprises any suitable method for producing a silica composite or any method described herein, for example, adjusting the pH of the mixture, removing water from the mixture and/or heating the mixture, adding a metal ion to the mixture, adding an organic solvent (eg, alcohol) to the mixture, storing the mixture for a suitable period of time, etc. or any combination of them.

Aspect 15. A method as defined in any one of aspects 1-14, wherein the silica component I comprises highly dispersed silica (pyrogenic silica), diatomaceous earth, silica-enriched clay (e.g., montmorillonite), or any combination thereof.

Aspect 16. The method defined according to any one of aspects 1-14, wherein the silica component I comprises Cab-o-sil ^® fumed silica, Aerosil ^® fumed silica, or any combination thereof .

Aspect 17 A method as defined in any one of aspects 1-14 wherein the silica component I is non-porous.

Aspect 18. The method defined according to any one of aspects 1-17, wherein the average size ratio of the silica component I is in any suitable range or any range given herein, for example, at least about 3:1, at least about 5:1, at least about 10:1, about 2:1 to about 50:1, about 3:1 to about 50:1, about 5:1 to about 50:1, etc.

Aspect 19. The method defined according to any one of aspects 1-18, wherein the BET specific surface area of the silica component I is in any suitable range or any range given herein, for example, from about 150 to about 600 m ² / g, from about 200 to about 500 m ² /g, etc.

Aspect 20. The method defined according to any one of aspects 1-19, wherein the silica component I is further characterized by an average particle size d50 in any suitable range or any range given herein, for example, from about 5 to about 500 nm, from about 10 to about 300 nm, etc.

Aspect 21 A method as defined in any one of aspects 1-20 wherein step (1) comprises combining (in any order) a titanium containing compound with a silica component I and a silica component II in a diluent or solvent.

Aspect 22 The method as defined in any one of aspects 1-21, further comprising the step of drying the silica composite, the step of calcining the silica composite, or both.

Aspect 23 A silica-based composite prepared by the method defined in any one of Aspects 1-22.

Aspect 24. Composite (composition) based on silicon dioxide, characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 25. A method for producing a supported chromium catalyst, comprising:

(1) combining (in any order) a chromium-containing compound and an optional titanium-containing compound with silica component I and silica component II in a diluent or solvent as defined in any of aspects 1-22 to form a mixture; And

(2) receiving in the specified mixture of compounds of chromium on a substrate; wherein:

supported chromium catalyst is characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 26. A method for producing a supported chromium catalyst, comprising:

performing step (1) and step (2) as defined according to any one of aspects 1-22; And

(3) combining (in any order) a chromium-containing compound and an optional titanium-containing compound with a silica-based composite to form a supported chromium catalyst; wherein:

supported chromium catalyst is characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 27. A method for producing a supported chromium catalyst, comprising:

combining (before calcination or during calcination) a chromium-containing compound and an optional titanium-containing compound with a silica-based composite as defined in aspect 23 or 24 to form a supported chromium catalyst; wherein:

supported chromium catalyst is characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 28. The method defined according to any one of aspects 25-27, wherein the catalyst contains any suitable amount of chromium, or an amount of chromium in any range given herein, for example, from about 0.1 to about 15% wt., from about 0.5 to about 5% wt., from about 0.5 to about 2.5% wt. etc. based on the total weight of the catalyst.

Aspect 29 The method as defined in any one of aspects 25-28, wherein the chromium compound comprises any suitable chromium(II) compound or any chromium(II) compound described herein, e.g., chromium(II) acetate, chromium chloride ( II), chromium (II) bromide, chromium (II) iodide, chromium (II) sulfate, etc. or any combination of them.

Aspect 30 The method as defined in any one of aspects 25-28, wherein the chromium compound comprises any suitable chromium(III) compound or any chromium(III) compound described herein, e.g., chromium(III) carboxylate, chromium naphthenate ( III), chromium (III) halide, chromium (III) sulfate, chromium (III) nitrate, chromium (III) dionate, chromium (III) acetate, chromium (III) acetylacetonate, chromium (III) chloride, chromium (III) bromide etc. or any combination of them.

Aspect 31. The method defined according to any one of aspects 25-30, wherein the catalyst contains any suitable amount of titanium or an amount of titanium in any range given herein, for example, from about 0.5 to about 10 wt.%, from about 1 to about 6% wt., from about 1.5 to about 5% wt. etc. based on the total weight of the catalyst.

Aspect 32. The method defined according to any one of aspects 25-31, wherein the titanium compound comprises any suitable titanium compound or any titanium compound described herein, e.g., a Ti(III) compound, a Ti(IV) compound, etc. . or any combination of them.

Aspect 33. The method defined according to any one of aspects 25-31, wherein the titanium compound comprises any suitable titanium compound or any titanium compound described herein, e.g., titanium alkoxide (e.g., titanium isopropoxide, titanium n-propoxide), halide or titanium oxohalide, titanium acetylacetonate complex, titanium triethanolamine complex, titanium carboxylate (eg, oxalate, citrate, lactate, etc.), etc. or their chelated or modified variants, as well as any combination thereof.

Aspect 34 The method as defined in any one of Aspects 25-33, further comprising the step of drying the chromium catalyst on the support.

Aspect 35 The method as defined in any one of Aspects 25-34, further comprising the step of calcining the supported chromium catalyst.

Aspect 36 A supported chromium catalyst prepared by the method defined in any one of Aspects 25-35.

Aspect 37. Chromium catalyst on a substrate containing a composite based on silicon dioxide and from about 0.1 to about 15% of the mass. chromium, while the specified catalyst is characterized by:

bulk density in the range of from about 0.08 to about 0.4 g/ml;

a total pore volume of from about 0.4 to about 2.5 ml/g;

specific surface area according to the BET method from about 175 to about 375 m ² /g; And

a maximum pore diameter of from about 10 to about 80 nm.

Aspect 38. The catalyst defined according to aspect 36 or 37, characterized in that the specified catalyst contains any suitable amount of chromium or the amount of chromium in any range given herein, for example, from about 0.5 to about 15% wt., from about 0.5 to about 5% wt., from about 0.5 to about 2.5% wt. etc. based on the total weight of the catalyst.

Aspect 39. The catalyst, defined according to any one of aspects 36-38, in which at least about 75 wt%, at least about 80 wt%, at least about 90 wt%, at least about 95 wt% . etc. chromium is present in an oxidation state of three or less (for example, the catalyst is pre-calcined).

Aspect 40. The catalyst defined according to any one of aspects 36-38, wherein at least about 30 wt%, at least about 50 wt%, at least about 60 wt%, at least about 80 wt% ., at least about 90% of the mass. etc. chromium is present as hexavalent chromium (for example, the catalyst is calcined).

Aspect 41. The catalyst defined according to any one of aspects 36-40, characterized in that said catalyst additionally contains any suitable amount of titanium or an amount of titanium in any range given herein, for example, from about 0.5 to about 10 wt%. ., from about 1 to about 6 wt. -%, from about 1.5 to about 5% of the mass. etc. based on the total weight of the catalyst.

Aspect 42. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the bulk density of the supported silica-chromium catalyst composite is independently within any suitable range or any range given herein, for example, from about 0.08 to about 0.35 g/ml, from about 0.1 to about 0.35 g/ml, from about 0.1 to about 0.32 g/ml, from about 0.12 to about 0.34 g/ml, etc.

Aspect 43. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, characterized in that the total pore volume of the supported silica- and chromium catalyst composite is independently in any suitable range or any range, given herein, for example, from about 0.5 to about 3.5 ml/g, from about 0.4 to about 1.5 ml/g, from about 0.5 to about 2 ml/g, from about 0 .5 to about 1.3 ml/g, etc.

Aspect 44. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the BET specific surface area of the supported silica-chromium catalyst composite is independently in any suitable range or any the range given herein, for example, from about 175 to about 360 m ² /g, from about 190 to about 375 m ² /g, from about 200 to about 360 m ² /g, etc.

Aspect 45. The method, the supported silica or chromium catalyst composite as defined in any of the preceding aspects, wherein the maximum pore diameter of the supported silica-chromium catalyst composite is independently within any suitable range or any range, described herein, for example, from about 10 to about 70 nm, from about 10 to about 50 nm, from about 15 to about 60 nm, from about 15 to about 50 nm, from about 17 to about 40 nm, from about 20 up to about 80 nm, from about 20 to about 50 nm, from about 25 to about 60 nm, etc.

Aspect 46. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, characterized in that the average pore diameter of the supported silica-chromium catalyst composite is independently in any suitable range or any range, given herein, for example, from about 8 to about 70 nm, from about 9 to about 50 nm, from about 9 to about 30 nm, from about 10 to about 50 nm, etc.

Aspect 47. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of total pore volume in pore diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm) or a percentage in any of the ranges provided herein, such as at least about 35%, at least about 40%, from about 35 to about 95 %, from about 40% to about 85%, etc.

Aspect 48. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of total pore volume in pore diameters in the range of 30 to 100 nm, or a percentage in any range given herein, for example, from about 0.5 to about 40%, from about 0.5 to about 35%, from about 1 to about 35%, from about 2 to about 35%, etc.

Aspect 49. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of total pore volume in pore diameters , less than or equal to 10 nm, or a percentage within any of the ranges provided herein, such as less than or equal to about 65%, less than or equal to about 60%, from about 5% to about 65%, from about 15% to about 55%, and etc.

Aspect 50. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of total pore volume in pore diameters , less than or equal to 5 nm, or a percentage in any range given herein, for example, less than or equal to about 25%, less than or equal to about 20%, from about 1 to about 25%, from about 2 to about 15%, and so on.

Aspect 51. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of total pore volume in pore diameters , less than or equal to 3 nm, or a percentage within any range given herein, such as less than or equal to about 8%, less than or equal to about 7%, less than or equal to about 6%, less than or equal to about 4%, and t .d.

Aspect 52. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst independently have any suitable pore volume in pores with diameters ranging from 10 to 50 nm (or in the range of 10 to 100 nm) or a pore volume in any range given herein, such as at least about 0.2 ml/g, at least about 0.3 ml/g, from about 0.2 to about 1.5 ml/g, from about 0.4 to about 1.3 ml/g, etc.

Aspect 53. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of total surface area in pore diameters in the range of 10 to 50 nm (or in the range of 10 to 100 nm), or a percentage in any of the ranges provided herein, such as at least about 15%, at least about 20%, from about 15 to about 65 %, from about 20 to about 60%, etc.

Aspect 54. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, characterized in that the silica-based composite and the supported chromium catalyst are independently characterized by any suitable percentage of surface area in pores with diameters, less than or equal to 5 nm, or a percentage within any range provided herein, such as less than or equal to about 50%, less than or equal to about 30%, from about 5 to about 50%, from about 5 to about 30%, etc. .d.

Aspect 55. The method, the silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, wherein the silica-based composite and the supported chromium catalyst independently have any suitable pore surface area with diameters ranging from 10 up to 50 nm (or in the range from 10 to 100 nm) or a pore surface area in any range given herein, for example, at least about 40 m ² /g, at least about 50 m ² /g, from about 40 to about 200 m ² /g, from about 60 to about 180 m ² /g, etc.

Aspect 56. The method, silica-based composite or supported chromium catalyst as defined in any of the preceding aspects, characterized in that the silica-based composite and the supported chromium catalyst independently have any suitable average (d50) particle size or average ( d50) particle size in any of the ranges given herein, for example, from about 10 to about 500 microns, from about 25 to about 250 microns, from about 40 to about 160 microns, etc.

Aspect 57. A process for polymerizing olefins comprising contacting a supported (activated) chromium catalyst as defined in any one of aspects 36-56 and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

Aspect 58 The olefin polymerization process defined in accordance with aspect 57, wherein a cocatalyst is used, including any suitable cocatalyst or any cocatalyst described herein, for example, an aluminoxane cocatalyst, an organoaluminum cocatalyst, an organoboron cocatalyst, and the like. or any combination of them.

Aspect 59. An olefin polymerization process defined according to aspect 57 or 58, wherein the catalyst has any suitable throughput or any of the throughputs recited herein, for example, from about 500 to about 5000 g/g, from about 800 to about 4000 g/g g, from about 1000 to about 3000 g/g, etc.

Aspect 60. A process for the polymerization of olefins as defined in any of aspects 57-59, wherein the olefin monomer comprises any olefin monomer described herein, for example, any C ₂ -C ₂₀ olefin.

Aspect 61. A process for polymerizing olefins as defined in any one of aspects 57-60, wherein the olefin monomer and the optional olefin comonomer independently comprise a C ₂ -C ₂₀ alpha olefin.

Aspect 62 An olefin polymerization process as defined in any one of Aspects 57-61, wherein the olefin monomer comprises ethylene.

Aspect 63 A process for the polymerization of olefins as defined in any one of aspects 57-62, wherein the catalyst is contacted with ethylene and an olefin comonomer comprising a C ₃ -C ₁₀ alpha olefin.

Aspect 64 An olefin polymerization process as defined in any one of aspects 57-63, wherein the catalyst is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 65 A process for the polymerization of olefins as defined in any one of Aspects 57-61, wherein the olefin monomer comprises propylene.

Aspect 66. An olefin polymerization process as defined in any one of aspects 57-65, wherein the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, or a combination thereof.

Aspect 67. An olefin polymerization process as defined in any one of aspects 57-66, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

Aspect 68. An olefin polymerization process as defined in any one of Aspects 57-67, wherein the polymerization reactor system comprises a slurry loop reactor.

Aspect 69 An olefin polymerization process as defined in any one of Aspects 57-68, wherein the polymerization reactor system comprises a single reactor.

Aspect 70. An olefin polymerization process as defined in any one of Aspects 57-68, wherein the polymerization reactor system comprises 2 reactors.

Aspect 71. An olefin polymerization process as defined in any one of Aspects 57-68, wherein the polymerization reactor system comprises more than 2 reactors.

Aspect 72 The process for polymerizing olefins as defined in any one of aspects 57-71, wherein the olefin polymer includes any of the olefin polymers described herein.

Aspect 73. An olefin polymerization process defined according to any one of aspects 57-64 or 66-72, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer .

Aspect 74 The process for polymerizing olefins as defined in any one of aspects 57-61 and 65-72, wherein the olefin polymer comprises a polypropylene homopolymer and/or a propylene-based copolymer.

Aspect 75. An olefin polymerization process as defined in any one of aspects 57-74, wherein the polymerization conditions include a polymerization reaction temperature in the range of about 60°C to about 120°C and a reaction pressure in the range of about 200 to about 1000 psig (from about 1.4 to about 6.9 MPa).

Aspect 76 A process for the polymerization of olefins as defined in any one of aspects 57-75, wherein the polymerization conditions are substantially constant, for example, to produce a particular grade of polymer.

Aspect 77. An olefin polymerization process as defined in any one of Aspects 57-76, wherein no hydrogen is added to the polymerization reactor system.

Aspect 78 An olefin polymerization process as defined in any one of aspects 57-76, wherein hydrogen is added to the polymerization reactor system.

Aspect 79. A process for the polymerization of olefins as defined in any one of aspects 57-78, wherein the olefin polymer has a density in any of the ranges recited herein, such as from about 0.90 to about 0.97, from about 0.92 to about 0.96, about 0.93 to about 0.955, about 0.94 to about 0.955 g/cc, and so ^on .

Aspect 80. An olefin polymerization process as defined in any one of aspects 57-79, wherein the olefin polymer has an HLMI in any of the ranges recited herein, such as from about 1 to about 80, from about 1 to about 50, from about 1 up to about 40, from about 2 to about 40 g/10 min, etc.

Aspect 81. A process for polymerizing olefins as defined in any one of aspects 57-80, wherein the olefin polymer has an I ₂₁ /I ₁₀ ratio in any of the ranges provided herein, such as from about 3 to about 12, from about 4 to about 10, from about 4.5 to about 9, etc.

Aspect 82. A process for polymerizing olefins as defined in any one of aspects 57-81, wherein the olefin polymer has a Mw/Mn ratio within any of the ranges provided herein, such as from about 5 to about 40, from about 7 to about 25, from about 8 to about 18, etc.

Aspect 83. A process for the polymerization of olefins as defined in any one of aspects 57-82, wherein the olefin polymer has an Mz/Mw ratio in any of the ranges recited herein, such as from about 5 to about 10, from about 5 to about 9, from about 6 to about 8, etc.

Aspect 84. A process for the polymerization of olefins as defined in any one of aspects 57-83, wherein the olefin polymer has an Mw in any of the ranges recited herein, for example, from about 150 to about 500 kg/mol, from about 200 to about 400 kg /mol, from about 180 to about 350 kg/mol, etc.

Aspect 85. An olefin polymerization process as defined in any one of aspects 57-84, wherein the olefin polymer has a CY-a parameter in any of the ranges provided herein, such as from about 0.1 to about 0.3, from about 0 .12 to about 0.28, from about 0.15 to about 0.25, and so on.

Aspect 86 An olefin polymer obtained from an olefin polymerization process as defined in any one of Aspects 57-85.

Aspect 87 An article of manufacture comprising a polymer as defined in Aspect 86.

Aspect 88. The article of manufacture defined in accordance with aspect 87, wherein said article is an agricultural film, an automobile part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane , household container, lining material, molded article, medical device or material, pipe, sheet or tape or toy.

Claims (95)

1. Chromium catalyst on the carrier, intended for the polymerization of olefins, containing a composite based on silicon dioxide and from 0.1 to 15% of the mass. chromium, while the specified catalyst is characterized by: bulk density from 0.08 to 0.4 g/ml; total pore volume from 0.4 to 2.5 ml/g; specific surface according to the BET method from 175 to 375 m ² /g; And a maximum pore diameter of 10 to 80 nm, where the maximum pore diameter refers to the location, on a pore diameter scale, of the highest point on the pore size distribution curve; And where from 0.5 to 40% of the total pore volume of the catalyst falls on pores with diameters in the range from 30 to 100 nm. 2. The catalyst according to claim 1, characterized in that from 2 to 35% of the total pore volume of the catalyst falls on pores with diameters in the range from 30 to 100 nm. 3. The catalyst according to claim 1, characterized in that: bulk density is from 0.1 to 0.35 g/ml; the total pore volume is from 0.5 to 2 ml/g; the specific surface according to the BET method is from 200 to 375 m ² /g; And the maximum pore diameter is from 15 to 50 nm. 4. The catalyst according to claim 1, characterized in that: the average pore diameter of the specified catalyst is from 10 to 50 nm; from 40 to 85% of the total pore volume of the catalyst falls on pores with diameters in the range from 10 to 50 nm; from 1 to 25% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 5 nm; And less than or 4% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 3 nm. 5. Catalyst according to claim 1, characterized in that: the specified catalyst contains from 0.5 to 5% of the mass. chromium; the specified catalyst additionally contains from 0.5 to 10% of the mass. titanium; And from 1 to 35% of the total pore volume of the catalyst falls on pores with diameters in the range from 30 to 100 nm. 6. The catalyst according to claim 1, in which at least 75% of the mass. chromium is present in an oxidation state of three or less. 7. The catalyst according to p. 1, in which at least 60% of the mass. chromium is present as hexavalent chromium. 8. Catalyst according to claim. 1, characterized in that the average pore diameter of the specified catalyst is from 10 to 50 nm. 9. Catalyst according to claim 1, characterized in that: the average pore diameter of said catalyst is from 9 to 30 nm. 10. Catalyst according to claim 1, characterized in that: the specified catalyst contains from 0.5 to 5% of the mass. chromium; And from 1 to 35% of the total pore volume of the catalyst falls on pores with diameters in the range from 30 to 100 nm. 11. The catalyst according to claim 3, characterized in that: the average pore diameter of the specified catalyst is from 10 to 50 nm; from 40 to 85% of the total pore volume of the catalyst falls on pores with diameters in the range from 10 to 50 nm; from 1 to 25% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 5 nm; And less than or 4% of the total pore volume of the catalyst is in pores with diameters less than or equal to 3 nm. 12. The catalyst according to claim 11, in which at least 90% of the mass. chromium is present in an oxidation state of three or less. 13. The catalyst according to claim 11, in which at least 80% of the mass. chromium is present as hexavalent chromium. 14. The catalyst according to claim 3, characterized in that: the specified catalyst contains from 0.5 to 5% of the mass. chromium; the specified catalyst additionally contains from 0.5 to 10% of the mass. titanium; And from 1 to 35% of the total pore volume of the catalyst falls on pores with diameters in the range from 30 to 100 nm. 15. The catalyst according to claim 3, in which at least 75% of the mass. chromium is present in an oxidation state of three or less. 16. The catalyst according to claim 3, in which at least 60% of the mass. chromium is present as hexavalent chromium. 17. A process for polymerizing olefins, comprising contacting the catalyst of claim 7 and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer. 18. The method according to claim 17, in which: the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof; And the olefin monomer is ethylene; And the olefin comonomer includes 1-butene, 1-hexene, 1-octene, or a mixture thereof. 19. The method of claim 17 wherein the olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer. 20. The method according to claim 19, in which the polymerization reactor system comprises a loop slurry reactor; And the productivity of the catalyst is from 500 to 5000 grams of polymer per gram of catalyst (g/g). 21. The method of claim 20, wherein the olefin polymer has: - HLMI in the range from 1 to 50 g/10 min; - the ratio of I ₂₁ /I ₁₀ in the range from 3 to 12; And - rheological width parameter CY-a in the range from 0.1 to 0.3. 22. Chromium catalyst on the media, designed for the polymerization of olefins, containing a composite based on silicon dioxide and from 0.1 to 15% of the mass. chromium, while the specified catalyst is characterized by: bulk density from 0.08 to 0.4 g/ml; total pore volume from 0.4 to 2.5 ml/g; specific surface according to the BET method from 175 to 375 m ² /g; And a maximum pore diameter of 10 to 80 nm, where the maximum pore diameter refers to the location, on a pore diameter scale, of the highest point on the pore size distribution curve; And where from 40 to 85% of the total pore volume of the catalyst falls on pores with diameters in the range from 10 to 50 nm. 23. The catalyst according to claim 22, characterized in that: the specified catalyst contains from 0.5 to 5% of the mass. chromium; And from 1 to 35% of the total pore volume of the catalyst falls on pores with diameters in the range from 30 to 100 nm. 24. The catalyst according to claim 22, characterized in that: bulk density is from 0.1 to 0.35 g/ml; the total pore volume is from 0.5 to 2 ml/g; the specific surface according to the BET method is from 200 to 375 m ² /g; And the maximum pore diameter is from 15 to 50 nm. 25. The catalyst according to claim 24, in which at least 75% of the mass. chromium is present in an oxidation state of three or less. 26. The catalyst according to claim 24, characterized in that: the average pore diameter of the catalyst is from 10 to 50 nm; from 1 to 25% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 5 nm; And less than or 4% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 3 nm. 27. The catalyst according to claim 26, in which at least 60% of the mass. chromium is present as hexavalent chromium. 28. A process for polymerizing olefins, comprising contacting the catalyst of claim 27 and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer. 29. The method according to claim 28, in which: the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof; And the olefin monomer is ethylene; And the olefin comonomer includes 1-butene, 1-hexene, 1-octene, or a mixture thereof. 30. Chromium catalyst on the media, designed for the polymerization of olefins, containing a composite based on silicon dioxide and from 0.1 to 15% of the mass. chromium, while the specified catalyst is characterized by: bulk density from 0.08 to 0.4 g/ml; total pore volume from 0.4 to 2.5 ml/g; specific surface according to the BET method from 175 to 375 m ² /g; And a maximum pore diameter of 10 to 80 nm, where the maximum pore diameter refers to the location, on a pore diameter scale, of the highest point on the pore size distribution curve; And where from 1 to 25% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 5 nm; And less than or 4% of the total pore volume of the catalyst falls on pores with diameters less than or equal to 3 nm. 31. The catalyst according to claim 30, in which at least 75% of the mass. chromium is present in an oxidation state of three or less. 32. The catalyst according to claim 30, characterized in that: bulk density is from 0.1 to 0.35 g/ml; the total pore volume is from 0.5 to 2 ml/g; the specific surface according to the BET method is from 200 to 375 m ² /g; And the maximum pore diameter is from 15 to 50 nm. 33. The catalyst according to claim 32, in which at least 60% of the mass. chromium is present as hexavalent chromium. 34. A process for polymerizing olefins, comprising contacting the catalyst of claim 33 and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to form an olefin polymer.

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